Principles of Environmental Chemistry

Principles of Environmental
Chemistry
Roy M Harrison
School of Geography, Earth and Environmental Sciences,
University of Birmingham, Birmingham, UK
ISBN-13: 978-0-85404-371-2
A catalogue record for this book is available from the British Library
r The Royal Society of Chemistry 2007
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Contents
Chapter 1 Introduction 1
R.M. Harrison
1.1 The Environmental Sciences 1
1.2 Environmental Chemical Processes 3
1.3 Environmental Chemicals 3
1.4 Units of Concentration 5
1.4.1 Atmospheric Chemistry 5
1.4.2 Soils and Waters 6
1.5 The Environment as a Whole 7
References 7
Chapter 2 Chemistry of the Atmosphere 8
P.S. Monks
2.1 Introduction 8
2.2 Sources of Trace Gases in the Atmosphere 10
2.3 Initiation of Photochemistry by Light 11
2.4 Tropospheric Chemistry 17
2.5 Tropospheric Oxidation Chemistry 20
2.5.1 Nitrogen Oxides and the Photostationary State 26
2.5.2 Production and Destruction of Ozone 28
2.5.3 Role of Hydrocarbons 35
2.5.4 Urban Chemistry 37
2.6 Night-Time Oxidation Chemistry 40
2.7 Ozone-Alkene Chemistry 46
2.8 Sulfur Chemistry 46
2.9 Halogen Chemistry 51
2.9.1 Tropospheric Halogens and Catalytic
Destruction of Ozone 56
vii
2.10 Stratospheric Chemistry 58
2.10.1 The Antarctic Ozone Hole 63
2.11 Summary 72
Questions 72
References 76
Chapter 3 Chemistry of Freshwaters 80
M.C. Graham and J.G. Farmer
3.1 Introduction 80
3.2 Fundamentals of Aquatic Chemistry 82
3.2.1 Introduction 82
3.2.2 Dissolution/Precipitation Reactions 91
3.2.3 Complexation Reactions in Freshwaters 94
3.2.4 Species Distribution in Freshwaters 97
3.2.5 Modelling Aquatic Systems 121
3.3 Case Studies 122
3.3.1 Acidification 122
3.3.2 Metals and Metalloids in Water 130
3.3.3 Historical Pollution Records and Perturbatory
Processes in Lakes 139
3.3.4 Nutrients in Water and Sediments 145
3.3.5 Organic Matter and Organic Chemicals
in Water 150
Questions and Problems 157
Further Reading 159
References 159
Chapter 4 Chemistry of the Oceans 170
S.J. de Mora
4.1 Introduction 170
4.1.1 The Ocean as a Biogeochemical Environment 170
4.1.2 Properties of Water and Seawater 173
4.1.3 Salinity Concepts 177
4.1.4 Oceanic Circulation 179
4.2 Seawater Composition and Chemistry 182
4.2.1 Major Constituents 182
4.2.2 Dissolved Gases 184
4.2.3 Nutrients 199
4.2.4 Trace Elements 201
4.2.5 Physico-Chemical Speciation 204
4.3 Suspended Particles and Marine Sediments 210
viii Contents
4.3.1 Description of Sediments and Sedimentary
Components 210
4.3.2 Surface Chemistry of Particles 213
4.3.3 Diagenesis 218
4.4 Physical and Chemical Processes in Estuaries 219
4.5 Marine Contamination and Pollution 223
4.5.1 Oil Slicks 223
4.5.2 Plastic Debris 226
4.5.3 Tributyltin 228
Questions 230
References 231
Chapter 5 The Chemistry of the Solid Earth 234
I.D. Pulford
5.1 Introduction 234
5.2 Mineral Components of Soil 238
5.2.1 Inputs 238
5.2.2 Primary Minerals 238
5.2.3 Secondary Minerals 240
5.2.4 Weathering Processes (See also Chapter 3) 246
5.3 Organic Components of Soil 248
5.4 Soil pH And Redox Potential 254
5.4.1 pH and Buffering 254
5.4.2 Soil Acidity 255
5.4.3 Soil Alkalinity 257
5.4.4 Influence of pH on Soils 258
5.4.5 Redox Potential 260
5.4.6 Reduction Processes in Soil 261
5.5 Chemical Reactions in Soil 263
5.5.1 Reactions in Soil Solution 263
5.5.2 Ion Exchange (Physisorption) 267
5.5.3 Ligand Exchange (Chemisorption) 271
5.5.4 Complexation/Chelation 273
5.5.5 Precipitation/Dissolution 273
5.5.6 Soil Processes 275
Questions 275
References 278
Chapter 6 Environmental Organic Chemistry 279
C.J. Halsall
6.1 Introduction 279
ix Contents
6.2 The Diversity of Organic Compounds 280
6.2.1 Identifying Sources of Hydrocarbons 282
6.3 The Fate of Organic Contaminants 284
6.4 Chemical Partitioning 284
6.4.1 Important Partitioning Coefficients 286
6.4.2 Temperature Dependence 292
6.4.3 Partition Maps 295
6.5 Chemical Transformation and Degradation 299
6.6 Chemical Transformation through Photochemistry 301
6.6.1 Light Absorption and the Beer-Lambert Law 302
6.6.2 Photolysis in Aqueous Systems 303
6.6.3 Photochemistry of Brominated Flame
Retardants (BFRs) 305
6.7 Conclusions 309
6.8 Questions 310
References 310
Chapter 7 Biogeochemical Cycling of Chemicals 314
R.M. Harrison
7.1 Introduction: Biogeochemical Cycling 314
7.1.1 Environmental Reservoirs 316
7.1.2 Lifetimes 317
7.2 Rates of Transfer between Environmental
Compartments 321
7.2.1 Air–Land Exchange 321
7.2.2 Air–Sea Exchange 324
7.3 Transfer in Aquatic Systems 330
7.4 Biogeochemical Cycles 333
7.4.1 Case Study 1: The Biogeochemical Cycle of
Nitrogen 335
7.4.2 Case Study 2: Aspects of Biogeochemical Cycle
of Lead 335
7.5 Behaviour of Long-Lived Organic Chemicals in the
Environment 340
Questions 344
References 345
Glossary 347
Subject Index 354
x Contents
Preface
While this book is in its first edition, it nonetheless has a lengthy
pedigree, which derives from a book entitled Understanding Our Envi-
ronment: An Introduction to Environmental Chemistry and Pollution,
which ran to three editions, the last of which was published in 1999.
Understanding Our Environment has proved very popular as a student
textbook, but changes in the way that the subject is taught had neces-
sitated its splitting into two separate books.
When Understanding Our Environment was first published, neither
environmental chemistry nor pollution was taught in many universities,
and most of those courses which existed were relatively rudimentary. In
many cases, no clear distinction was drawn between environmental
chemistry and pollution and the two were taught largely hand in hand.
Nowadays, the subjects are taught in far more institutions and in a far
more sophisticated way. There is consequently a need to reflect these
changes in what would have been the fourth edition of Understanding
Our Environment, and after discussion with contributors to the third
edition and with the Royal Society of Chemistry, it was decided to divide
the former book into two and create new books under the titles respec-
tively of An Introduction to Pollution Science and Principles of Environ-
mental Chemistry. Because of the authoritative status of the authors of
Understanding Our Environment and highly positive feedback which we
had received on the book, it was decided to retain the existing chapters
where possible while updating the new structure to enhance them
through the inclusion of further chapters.
This division of the earlier book into two new titles is designed to
accommodate the needs of what are now two rather separate markets.
An Introduction to Pollution Science is designed for courses within
degrees in environmental sciences, environmental studies and related
areas including taught postgraduate courses, which are not embedded in
a specific physical science or life science discipline such as chemistry,
v
physics or biology. The level of basic scientific knowledge assumed of
the reader is therefore only that of the generalist and the book should be
accessible to a very wide readership including those outside of the
academic world wishing to acquire a broadly based knowledge of
pollution phenomena. The second title, Principles of Environmental
Chemistry assumes a significant knowledge of chemistry and is aimed
far more at courses on environmental chemistry which are embedded
within chemistry degree courses. The book will therefore be suitable for
students taking second or third year option courses in environmental
chemistry or those taking specialised Masters’ courses, having studied
the chemical sciences at first-degree level.
In this volume I have been fortunate to retain the services of a number
of authors from Understanding Our Environment. The approach has
been to update chapters from that book where possible, although some
of the new authors have decided to take a completely different ap-
proach. The book initially deals with the atmosphere, freshwaters, the
oceans and the solid earth as separate compartments. There are certain
common crosscutting features such as non-ideal solution chemistry, and
where possible these are dealt with in detail where they first occur, with
suitable cross-referencing when they re-appear at later points. Chemicals
in the environment do not respect compartmental boundaries, and
indeed many important phenomena occur as a result of transfers
between compartments. The book therefore contains subsequent chap-
ters on environmental organic chemistry, which emphasises the complex
behaviour of persistent organic pollutants, and on biogeochemical cy-
cling of pollutants, including major processes affecting both organic and
inorganic chemical species.
I am grateful to the authors for making available their great depth and
breadth of experience to the production of this book and for tolerating
my many editorial quibbles. I believe that their contributions have
created a book of widespread appeal, which will find many eager readers
both on taught courses and in professional practice.
Roy M. Harrison
Birmingham, UK
vi Preface
CHAPTER 1
Introduction
ROY M. HARRISON
Division of Environmental Health and Risk Management, School of
Geography, Earth and Environmental Sciences, University of Birmingham,
Edgbaston, B15 2TT, Birmingham, UK
1.1 THE ENVIRONMENTAL SCIENCES
It may surprise the student of today to learn that ‘the environment’ has not
always been topical and indeed that environmental issues have become a
matter of widespread public concern only over the past 20 years or so.
Nonetheless, basic environmental science has existed as a facet of human
scientific endeavour since the earliest days of scientific investigation. In the
physical sciences, disciplines such as geology, geophysics, meteorology,
oceanography, and hydrology, and in the life sciences, ecology, have a long
and proud scientific tradition. These fundamental environmental sciences
underpin our understanding of the natural world and its current-day
counterpart perturbed by human activity, in which we all live.
The environmental physical sciences have traditionally been concerned
with individual environmental compartments. Thus, geology is centred
primarily on the solid earth, meteorology on the atmosphere, oceanog-
raphy upon the salt-water basins, and hydrology upon the behaviour of
freshwaters. In general (but not exclusively) it has been the physical
behaviour of these media which has been traditionally perceived as
important. Accordingly, dynamic meteorology is concerned primarily
with the physical processes responsible for atmospheric motion, and
climatology with temporal and spatial patterns in physical properties of
the atmosphere (temperature, rainfall, etc.). It is only more recently that
chemical behaviour has been perceived as being important in many of
these areas. Thus, while atmospheric chemical processes are at least as
important as physical processes in many environmental problems such as
stratospheric ozone depletion, the lack of chemical knowledge has been
1
extremely acute as atmospheric chemistry (beyond major component
ratios) only became a matter of serious scientific study in the 1950s.
There are two major reasons why environmental chemistry has flourished
as a discipline only rather recently. Firstly, it was not previously perceived
as important. If environmental chemical composition is relatively invariant
in time, as it was believed to be, there is little obvious relevance to
continuing research. Once, however, it is perceived that composition is
changing (e.g. CO
2
in the atmosphere;
137
Cs in the Irish Sea) and that such
changes may have consequences for humankind, the relevance becomes
obvious. The idea that using an aerosol spray in your home might damage
the stratosphere, although obvious to us today, would stretch the credulity
of someone unaccustomed to the concept. Secondly, the rate of advance
has in many instances been limited by the available technology. Thus, for
example, it was only in the 1960s that sensitive reliable instrumentation
became widely available for measurement of trace concentrations of metals
in the environment. This led to a massive expansion in research in this field
and a substantial downward revision of agreed typical concentration levels
due to improved methodology in analysis. It was only as a result of James
Lovelock’s invention of the electron capture detector that CFCs were
recognised as minor atmospheric constituents and it became possible to
monitor increases in their concentrations (see Table 1). The table exempli-
fies the sensitivity of analysis required since concentrations are at the ppt
level (1 ppt is one part in 10
12
by volume in the atmosphere) as well as the
substantial increasing trends in atmospheric halocarbon concentrations, as
measured up to 1990. The implementation of the Montreal Protocol, which
requires controls on production of CFCs and some other halocarbons, has
led to a slowing and even a reversal of annual concentration trends since
1992 (see Table 1).
Table 1 Atmospheric halocarbon concentrations and trends
a
Halocarbon
Concentration (ppt) Annual change (ppt)
Lifetime (years) Pre-industrial 2000 To 1990 1999–2000
CCl
3
F (CFC-11) 0 261 þ9.5 À1.1 50
CCl
2
F
2
(CFC-12) 0 543 þ16.5 þ2.3 102
CClF
3
(CFC-113) 0 3.5 400
C
2
Cl
2
F
4
(CFC-113) 0 82 þ4–5 À0.35 85
C
2
Cl
2
F
4
(CFC-114) 0 16.5 300
C
2
ClF
5
(CFC-115) 0 8.1 þ0.16 1700
CCl
4
0 96.1 þ2.0 À0.94 42
CH
3
CCl
3
0 45.4 þ6.0 À8.7 4.9
a
Data from: World Meteorological Organization, Scientific Assessment of Ozone Depletion: 2002,
WHO, Geneva, 2002.
2 Chapter 1
1.2 ENVIRONMENTAL CHEMICAL PROCESSES
The chemical reactions affecting trace gases in the atmosphere generally
have quite significant activation energies and thus occur on a timescale of
minutes, days, weeks, or years. Consequently, the change to such chem-
icals is determined by the rates of their reactions and atmospheric chem-
istry is intimately concerned with the study of reactions kinetics. On the
other hand, some processes in aquatic systems have very low activation
energies and reactions occur extremely rapidly. In such circumstances,
provided there is good mixing, the chemical state of matter may be
determined far more by the thermodynamic properties of the system than
by the rates of chemical processes and therefore chemical kinetics.
The environment contains many trace substances at a wide range of
concentrations and under different temperature and pressure conditions.
At very high temperatures such as can occur at depth in the solid earth,
thermodynamics may also prove important in determining, for example,
the release of trace gases from volcanic magma. Thus, the study of
environmental chemistry requires a basic knowledge of both chemical
thermodynamics and chemical kinetics and an appreciation of why one
or other is important under particular circumstances. As a broad
generalisation it may be seen that much of the chapter on atmospheric
chemistry is dependent on knowledge of reaction rates and underpinned
by chemical kinetics, whereas the chapters on freshwater and ocean
chemistry and the aqueous aspects of the soils are very much concerned
with equilibrium processes and hence chemical thermodynamics. It
should not however be assumed that these generalisations are univer-
sally true. For example, the breakdown of persistent organic pollutants
in the aquatic environment is determined largely by chemical kinetics,
although the partitioning of such substances between different environ-
mental media (air, water, soil) is determined primarily by their thermo-
dynamic properties and to a lesser degree by their rates of transfer.
1.3 ENVIRONMENTAL CHEMICALS
This book is not concerned explicitly with chemicals as pollutants. This is
a topic covered by a companion volume on Pollution Science. This book,
however, is nonetheless highly relevant to the understanding of chemical
pollution phenomena. The major areas of coverage are as follows:
(i) The chemistry of freshwaters. Freshwaters comprise three different
major components. The first is the water itself, which inevitably
contains dissolved substances, both inorganic and organic. Its
properties are to a very significant degree determined by the
3 Introduction
inorganic solutes, and particularly those which determine its hard-
ness and alkalinity. The second component is suspended sediment,
also referred to as suspended solids. These are particles, which are
sufficiently small to remain suspended with the water column for
significant periods of time where they provide a surface onto which
dissolved substances may deposit or from which material may
dissolve. The third major component of the system is the bottom
sediment. This is an accumulation of particles and associated pore
water, which has deposited out of the water column onto the bed
of the stream, river, or lake. The size of the sediment grains is
determined by the speed and turbulence of the water above. A fast-
flowing river will retain small particles in suspension and only large
particles (sand or gravel) will remain on the bottom. In relatively
stagnant lake water, however, very small particles can sediment
out and join the bottom sediment. In waters of this kind, sediment
accumulates over time and therefore the surface sediments in
contact with the water column contain recently deposited material
while the sediment at greater depths contains material deposited
tens or hundreds of years previously. In the absence of significant
mixing by burrowing organisms, the depth profile of some chem-
icals within a lake bottom sediment can provide a very valuable
historical record of inputs of that substance to the lake. Ingenious
ways have been devised for determining the age of specific bands of
sediment. While the waters at the surface of a lake are normally in
contact with the atmosphere and therefore well aerated, water at
depth and the pore water within the bottom sediment may have a
very poor oxygen supply and therefore become oxygen-depleted
and are then referred to as anoxic or anaerobic. This can affect the
behaviour of redox-active chemicals such as transition elements,
and therefore the redox properties of freshwaters and their sedim-
ents are an important consideration.
(ii) Salt waters. The waters of seas and oceans differ substantially
from freshwaters by virtue of their very high content of dissolved
inorganic material and their very great depth at some points on
the globe. These facets confer properties, which although over-
lapping with those of freshwaters, can be quite distinct. Some
inorganic components will behave quite differently in a very high
salinity environment than in a low ionic strength freshwater.
Historically, therefore, the properties of seawater have tradition-
ally been studied separately from those of freshwaters and are
presented separately, although the important overlaps such as in
the area of carbonate equilibria are highlighted.
4 Chapter 1
(iii) The chemistry of soils and rocks. There are very significant overlaps
with freshwater chemistry but the main differences arise from the
very large quantities of solid matter providing very large surfaces
and often restricting access of oxygen so that conditions readily
become anoxic. However, many of the basic issues such as carbon-
ate equilibria and redox properties overlap very strongly with the
field of freshwater chemistry. Soils can, however, vary very greatly
according to their location and the physical and chemical processes
which have affected them during and since their formation.
(iv) Environmental organic chemistry. Much of the traditional study
of the aquatic and soil environment has been concerned with its
inorganic constituents. Increasingly, however, it is recognised
that organic matter plays a very important role both in terms
of the contribution of natural organic substances to the proper-
ties of waters and soils, but also that specific organic compounds,
many of them deriving from human activity, show properties in
the environment which are not easily understood from traditional
approaches and therefore these have become a rather distinct
area of study.
(v) Atmospheric chemistry. The atmosphere contains both gas phase
and particulate material. The study of both is important and the
two interact very substantially. However, as outlined previously,
chemical processes in the atmosphere tend to be very strongly
influenced by kinetic factors, and to a large extent are concerned
with rather small molecules, which play only a minor part in the
chemistry of the aquatic environment or solid earth. Inevitably,
there are important processes at the interface between the atmos-
phere and the land surface or oceans, but these are dealt with more
substantially in the companion volume on Pollution Science.
1.4 UNITS OF CONCENTRATION
1.4.1 Atmospheric Chemistry
Concentrations of trace gases and particles in the atmosphere can be
expressed as mass per unit volume, typically mg m
À3
. The difficulty with
this unit is that it is not independent of temperature and pressure. Thus, as
an airmass becomes warmer or colder, or changes in pressure, so its
volume will change, but the mass of the trace gas will not. Therefore, air
containing 1 mg m
À3
of sulfur dioxide in air at 01C will contain less than 1
mg m
À3
of sulfur dioxide in air if heated to 251C. For gases (but not
particles), this difficulty is overcome by expressing the concentration of
5 Introduction
the trace gas as a volume mixing ratio. Thus, 1 cm
3
of pure sulfur dioxide
dispersed in 1 m
3
of polluted air would be described as a concentration of
1 ppm. Reference to the gas laws tells us that not only is this one part per
10
6
by volume, it is also one molecule in 10
6
molecules and one mole in
10
6
moles, as well as a partial pressure of 10
À6
atm. Additionally, if the
temperature and pressure of the airmass change, this affects the trace gas
in the same way as the air in which it is contained and the volume-mixing
ratio does not change. Thus, ozone in the stratosphere is present in air at
considerably higher mixing ratios than in the lower atmosphere (tropo-
sphere), but if the concentrations are expressed in mg m
À3
they are little
different because of the much lower density of air at stratospheric
attitudes. Chemical kineticists often express atmospheric concentrations
in molecules per cubic centimetre (molec cm
À3
), which has the same
problem as the mass per unit volume units.
Worked Example
The concentration of nitrogen dioxide in polluted air is 85 ppb. Express
this concentration in units of mg m
À3
and molec cm
À3
if the air
temperature is 201C and the pressure 1005 mb (1.005 Â 10
5
Pa). Relative
molecular mass of NO
2
is 46; Avogadro number is 6.022 Â 10
23
.
The concentration of NO
2
is 85 mL m
À3
. At 201C and 1005 mb,
85 mL NO
2
weigh 46 Â
85 Â10
À6
22:41
Â
273
293
Â
1005
1013
¼ 161 Â10
À6
g
NO
2
concentration ¼ 161 mg m
À3
This is equivalent to 161 pg cm
À3
, and
161 pg NO
2
contain 6:022 Â10
23
Â
161 Â10
À12
46
¼ 2:1 Â10
12
molecules
and NO
2
concentration ¼ 2.1 Â 10
12
molec cm
À3
.
1.4.2 Soils and Waters
Concentrations of pollutants in soils are most usually expressed in mass
per unit mass, for example, milligrams of lead per kilogram of soil.
Similarly, concentrations in vegetation are also expressed in mg kg
À1
or
mg kg
À1
. In the case of vegetation and soils, it is important to distinguish
6 Chapter 1
between wet and dry weight concentrations, in other words, whether the
kilogram of vegetation or soil is determined before or after drying. Since
the moisture content of vegetation can easily exceed 50%, the data can
be very sensitive to this correction.
In aquatic systems, concentrations can also be expressed as mass per
unit mass and in the oceans some trace constituents are present at
concentrations of ng kg
À1
or mg kg
À1
. More often, however, sample sizes
are measured by volume and concentrations expressed as ng L
À1
or mg
L
À1
. In the case of freshwaters, especially, concentrations expressed as
mass per litre will be almost identical to those expressed as mass per
kilogram. As a kind of shorthand, however, water chemists sometimes
refer to concentrations as if they were ratios by weight, thus, mg L
À1
are
expressed as ppm, mg L
À1
as ppb and ng L
À1
as ppt. This is unfortunate
as it leads to confusion with the same units used in atmospheric
chemistry with a quite different meaning.
1.5 THE ENVIRONMENT AS A WHOLE
A facet of the chemically centred study of the environment is a greater
integration of the treatment of environmental media. Traditional bound-
aries between atmosphere and waters, for example, are not a deterrent to
the transfer of chemicals (in either direction), and indeed many important
and interesting processes occur at these phase boundaries.
In this book, the treatment first follows traditional compartments
(Chapters 2, 3, 4, and 5) although some exchanges with other compart-
ments are considered. Fundamental aspects of the science of atmosphere,
waters, and soils are described, together with current environmental
questions, exemplified by case studies. Subsequently, the organic chem-
istry of the environment is considered in Chapter 6, and quantitative
aspects of transfer across phase boundaries are described in Chapter 7,
where examples are given of biogeochemical cycles.
REFERENCES
1. For readers requiring knowledge of basic chemical principles R.M.
Harrison and S.J. de Mora, Introductory Chemistry for the Environmen-
tal Sciences, 2nd edn, Cambridge University Press, Cambridge, 1996.
2. For more detailed information upon pollution phenomena Pollution:
Causes, Effects and Control, 4th edn, R.M. Harrison (ed), RSC,
Cambridge, 2001 or R.M. Harrison (ed), Introduction to Pollution
Science, RSC, Cambridge, 2006.
7 Introduction
CHAPTER 2
Chemistry of the Atmosphere
PAUL S. MONKS
Department of Chemistry, University of Leicester, LE1 7RH, Leicester, UK
2.1 INTRODUCTION
The thin gaseous envelope that surrounds our planet is integral to the
maintenance of life on earth. The composition of the atmosphere is
predominately determined by biological processes acting in concert with
physical and chemical change. Though the concentrations of the major
atmospheric constituents oxygen and nitrogen remain the same, the
concentration of trace species, which are key to many atmospheric
processes are changing. It is becoming apparent that man’s activities
are beginning to change the composition of the atmosphere over a range
of scales, leading to, for example, increased acid deposition, local and
regional ozone episodes, stratospheric ozone loss and potentially climate
change. In this chapter, we will look at the fundamental chemistry of the
atmosphere derived from observations and their rationalisation.
In order to understand the chemistry of the atmosphere we need to be
able to map the different regions of the atmosphere. The atmosphere can
be conveniently classified into a number of different regions which are
distinguished by different characteristics of the dynamical motions of
the air (see Figure 1). The lowest region, from the earth’s surface to the
tropopause at a height of 10–15 km, is termed the troposphere. The
troposphere is the region of the active weather systems which determine
the climate at the surface of the earth. The part of the troposphere at the
earth’s surface, the planetary boundary layer, is that which is influenced
on a daily basis by the underlying surface.
Above the troposphere lies the stratosphere, a quiescent region of the
atmosphere where vertical transport of material is slow and radiative
transfer of energy dominates. In this region lies the ozone layer which
8
Figure 1 Vertical structure of the atmosphere. The vertical profile of temperature can be
used to define the different atmospheric layers
9 Chemistry of the Atmosphere
has an important property of absorbing ultraviolet (UV) radiation from
the sun, which would otherwise be harmful to life on earth. The
stratopause at approximately 50 km altitude marks the boundary
between the stratosphere and the mesosphere, which extends upwards
to the mesopause at approximately 90 km altitude. The mesosphere is a
region of large temperature extremes and strong turbulent motion in the
atmosphere over large spatial scales.
1
Above the mesopause is a region characterised by a rapid rise in
temperature, known as the thermosphere.
2
In the thermosphere, the
atmospheric gases, N
2
and O
2
, are dissociated to a significant extent into
atoms so the mean molecular mass of the atmospheric species falls. The
pressure is low and thermal energies are significantly departed from
the Boltzmann equilibrium. Above 160 km gravitational separation of
the constituents becomes significant and atomic hydrogen atoms, the
lightest neutral species, moves to the top of the atmosphere. The other
characteristic of the atmosphere from mesosphere upwards is that above
60 km, ionisation is important. This region is called the ionosphere. It is
subdivided into three regimes, the D, E and F region, characterised by
the types of dominant photo ionisation.
3
With respect to atmospheric chemistry, though there is a great deal of
interesting chemistry taking place higher up in the atmosphere,
1–3
we
shall focus in the main on the chemistry of the troposphere and strato-
sphere.
2.2 SOURCES OF TRACE GASES IN THE ATMOSPHERE
As previously described, the troposphere is the lowest region of the
atmosphere extending from the earth’s surface to the tropopause at 10–18
km. About 90% of the total atmospheric mass resides in the troposphere
and the greater part of the trace gas burden is found there. The tropo-
sphere is well mixed and its bulk composition is 78% N
2
, 21% O
2
, 1% Ar
and 0.036% CO
2
with varying amounts of water vapour depending on
temperature and altitude. The majority of the trace species found in the
atmosphere are emitted into the troposphere from the surface and are
subject to a complex series of chemical and physical transformations.
Trace species emitted directly into the atmosphere are termed to have
primary sources, e.g. trace gases such as SO
2
, NO and CO. Those trace
species formed as a product of chemical and/or physical transformation
of primary pollutants in the atmosphere, e.g. ozone, are referred to as
having secondary sources or being secondary species.
Emissions into the atmosphere are often broken down into broad
categories of anthropogenic or ‘‘man-made sources’’ and biogenic or
10 Chapter 2
natural sources with some gases also having geogenic sources. Table 1
lists a selection of the trace gases and their major sources.
4
For the
individual emission of a primary pollutant there are a number of factors
that need to be taken into account in order to estimate the emission
strength, these include the range and type of sources and the spatio- and
temporal-distribution of the sources. Often these factors are compiled
into the so-called emission inventories that combine the rate of emission
of various sources with the number and type of each source and the time
over which the emissions occur. Figure 2 shows the UK emission
inventory for a range of primary pollutants ascribed to different source
categories (see caption of Figure 2). It is clear from the data in Figure 2
that, for example, SO
2
has strong sources from public power generation
whereas ammonia has strong sources from agriculture. Figure 3 shows
the (2002) 1 Â 1 km emission inventories for SO
2
and NO
2
for the UK.
In essence, the data presented in Figure 2 has been apportioned spatially
according to magnitude of each source category (e.g. road transport,
combustion in energy production and transformation, solvent use). For
example, in Figure 3a, the major road routes are clearly visible, showing
NO
2
has a major automotive source (cf. Figure 2). It is possible to scale
the budgets of many trace gases to a global scale.
It is worth noting that there are a number of sources that do not occur
within the boundary layer (the decoupled lowest layer of the tropo-
sphere, see Figure 1), such as lightning production of nitrogen oxides
and a range of pollutants emitted from the combustion-taking place in
aircraft engines. The non-surface sources often have a different chemical
impact owing to their direct injection into the free troposphere (the part
of the troposphere that overlays the boundary layer).
In summary, there are a range of trace species present in the atmos-
phere with a myriad of sources varying both spatially and temporally.
5
It is the chemistry of the atmosphere that acts to transform the primary
pollutants into simpler chemical species.
2.3 INITIATION OF PHOTOCHEMISTRY BY LIGHT
Photodissociation of atmospheric molecules by solar radiation plays a
fundamental role in the chemistry of the atmosphere. The photodisso-
ciation of trace species such as ozone and formaldehyde contributes to
their removal from the atmosphere, but probably the most important
role played by these photoprocesses is the generation of highly reactive
atoms and radicals. Photodissociation of trace species and the subse-
quent reaction of the photoproducts with other molecules is the prime
initiator and driver for the bulk of atmospheric chemistry.
11 Chemistry of the Atmosphere
Table 1 Natural and anthropogenic sources of a selection of trace gases
Compound Natural sources Anthropogenic sources
Carbon-containing compounds
Carbon dioxide
(CO
2
)
Respiration; oxidation of
natural CO; destruction of
forests
Combustion of oil, gas, coal
and wood; limestone
burning
Methane (CH
4
) Enteric fermentation in wild
animals; emissions from
swamps, bogs, etc.,
natural wet land areas;
oceans
Enteric fermentation in
domesticated ruminants;
emissions from paddy
fields; natural gas leakage;
sewerage gas; colliery gas;
combustion sources
Carbon monoxide
(CO)
Forest fires; atmospheric
oxidation of natural
hydrocarbons and
methane
Incomplete combustion of
fossil fuels and wood, in
particular motor vehicles,
oxidation of
hydrocarbons; industrial
processes; blast furnaces
Light paraffins,
C
2
–C
6
Aerobic biological source Natural gas leakage; motor
vehicle evaporative
emissions; refinery
emissions
Olefins, C
2
–C
6
Photochemical degradation
of dissolved oceanic
organic material
Motor vehicle exhaust; diesel
engine exhaust
Aromatic
hydrocarbons
Insignificant Motor vehicle exhaust;
evaporative emissions;
paints, gasoline, solvents
Terpenes (C
10
H
16
) Trees (broadleaf and
coniferous); plants
CFCs and HFCs None Refrigerants; blowing agents;
propellants
Nitrogen-containing trace gases
Nitric oxide (NO) Forest fires; anaerobic
processes in soil; electric
storms
Combustion of oil, gas and
coal
Nitrogen dioxide
(NO
2
)
Forest fires; electric storms Combustion of oil, gas and
coal; atmospheric
transformation of NO
Nitrous oxide
(N
2
O)
Emissions from denitrifying
bacteria in soil; oceans
Combustion of oil and coal
Ammonia (NH
3
) Aerobic biological source in
soil. Breakdown of amino
acids in organic waste
material
Coal and fuel oil combustion;
waste treatment
Sulfur-containing trace gases
Dimethyl sulfide
(DMS)
Phytoplankton Landfill gas
Sulfur dioxide
(SO
2
)
Oxidation of H
2
S; volcanic
activity
Combustion of oil and coal;
roasting sulfide ores
(Continued )
12 Chapter 2
Table 1 (Continued )
Compound Natural sources Anthropogenic sources
Other minor trace gases
Hydrogen Oceans, soils; methane
oxidation, isoprene and
terpenes via HCHO
Motor vehicle exhaust;
oxidation of methane via
formaldehyde (HCHO)
Ozone In the stratosphere; natural
NOÀNO
2
conversion
Man-made NOÀNO
2
conversion; supersonic
aircraft
Water (H
2
O) Evaporation from oceans Insignificant
Source: From ref. 4.
1. Public power, cogeneration
and district heating
2. Commercial, institutional and
residential combustion
3. Industrial combustion
4. Production processes
5. Extraction and distribution of
fossil fuels
6. Solvent use
7. Road transport
8. Other mobile sources and
machinery
9. Waste treatment and
disposal
10. Agriculture
11. Nature
Sources of emission in the UK
SO
2
NO
x
NMVVOC CH
4
CO CO
2
N
2
O NH
3
6
11
4
7 1
3
2
1
7
3
9
2
9
10
10
10
7
2
7
8
1
2
3
1
4
7
9
2
7
Figure 2 UK emission statistics by UNECE source category (1) Combustion in Energy
production and transformation; (2) Combustion in commercial, institutional,
residential and agriculture; (3) Combustion in industry; (4) Production proc-
esses; (5) Extraction and distribution of fossil fuels; (6) Solvent use; (7) Road
transport; (8) Other transport and mobile machinery; (9) Waste treatment and
disposal; (10) Agriculture, forestry and land use change; (11) Nature
13 Chemistry of the Atmosphere
The light source for photochemistry in the atmosphere is the sun. At
the top of the atmosphere there is ca. 1370 W m
À2
of energy over a wide
spectral range, from X-rays through the visible to longer wavelength. By
the time the incident light reaches the troposphere much of the more
energetic, shorter wavelength light has been absorbed by molecules such
as oxygen, ozone and water vapour or scattered higher in the atmos-
phere. Typically, in the surface layers, light of wavelengths longer than
290 nm are available (see Figure 4). In the troposphere, the wavelength
at which the intensity of light drops to zero is termed the atmospheric
cut-off. For the troposphere, this wavelength is determined by the
overhead stratospheric ozone column (absorbs ca. l r 310 nm) and
the aerosol loading. In the mid- to upper-stratosphere, the amount of O
3
absorption in the ‘‘window’’ region at 200 nm between the O
3
and O
2
absorptions controls the availability of short-wavelength radiation that
can photodissociate molecules that are stable in the troposphere. In the
stratosphere (at 50 km), there is typically no radiation of wavelength
shorter than 183 nm.
The light capable of causing photochemical reactions is termed the
actinic flux, F
l
(l) (cm
À2
s
À1
nm
À1
), which is also known as the scalar
Figure 3 UK emission maps (2002) on a 1 Â 1 km grid for (a) NO
2
and (b) SO
2
and in
kg (data from UK NAIE, http://www.naei.org.uk/)
14 Chapter 2
intensity or spherical radiant flux, viz
F
l
ðlÞ ¼
Z
L
l
ðl; W; jÞ do ð2:1Þ
where L
l
(l) (cm
À2
s
À1
sr
À1
nm
À1
) denotes the spectral photon radiance,
o is the solid angle and (W, j) are the polar and azimuthal angles of
incidence of the radiation interacting with the molecule of interest. In
essence, all angles of incident light must be considered when measuring
or calculating the actinic flux (i.e. W ¼ 0–1801, o ¼ 0–3601). Photolysis
rates are often expressed as a first-order loss process, e.g. in the
photolysis of NO
2
NO
2
þ hn -NO þ O(
3
P) (2.2)
i.e.
À
d½NO
2
Š
dt
¼ j
2:2
½NO
2
Š ð2:3Þ
where the photolysis frequency, j, can be expressed as
j ¼
Z
l
max
l
min
sðl; TÞfðl; TÞF
l
ðlÞdl ð2:4Þ
O
3
Energy curve for blackbody at 6000K
Solar irradiance curve outside atmosphere
Solar irradiance curve at sea level for a
zenith angle of 0°
O
2
H
2
O
O
2
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O H
2
O
CO
2
2.5
2.0
1.5
1.0
0.5
0
0 200 600 1000 1600 2000 2600 3000
Visible
Infrared
O
3
UV
Wavelength (nm)
S
o
l
a
r

f
l
u
x

(
W

m
-
2

n
m
-
1
)
Figure 4 Solar flux outside the atmosphere and at sea level, respectively. The emission of a
blackbody at 6000 K is included for comparison. The species responsible for light
absorption in the various regions (O
2
, H
2
O, etc.) are also shown (after ref. 60)
15 Chemistry of the Atmosphere
where s the absorption cross-section (cm
2
), f the quantum yield of the
photoproducts and T the temperature. Figure 5 shows a typical meas-
ured photolysis rate for NO
2
(reaction (2.2)) in the atmosphere. The
photolysis rate reaches a maximum at solar noon concomitant with the
maximum in solar radiation.
Example for the calculation of photolysis rates
From the following data calculate the photolysis rate of O
3
into
O(
1
D) at T ¼ 298 K.
Wavelength (nm) F(l) (photon cm
À2
s
À1
) s (cm
2
molec
À1
) f
295–300 2.66 Â 10
13
59.95 Â 10
À20
1.0
300–305 4.20 Â 10
14
26.50 Â 10
À20
1.0
305–310 1.04 Â 10
15
15.65 Â 10
À20
0.83
310–315 1.77 Â 10
15
7.95 Â 10
À20
0.26
315–320 1.89 Â 10
15
4.15 Â 10
À20
0.21
The data used represent a gross approximation, owing to the large
changes in all the quantities in the region of the atmospheric cut-off, but
0.E+00
1.E-03
2.E-03
3.E-03
4.E-03
5.E-03
6.E-03
7.E-03
8.E-03
9.E-03
04:00 06:00 08:00 10:00 12:00 14:00 16:00 18:00 20:00 22:00
time (UT)/ h
2
π

s
r

j

(

N
O
2
)
/

s
-
1
J214 (clear)
J224 (cloudy)
Figure 5 Diurnal profile of j(NO
2
) (reaction (2.2)) measured on a clear sky and cloudy
day
61
16 Chapter 2
are illustrative of the method and controlling quantities for ozone
photolysis.
The most commonly used form of Equation (2.4) becomes
jðs
À1
Þ ¼
X
l
max
l
min
s
av
ðlÞf
av
ðlÞF
av
ðlÞ
The av denotes that average of wavelength intervals. Therefore, j ¼
3.14 Â 10
À4
s
À1
.
2.4 TROPOSPHERIC CHEMISTRY
In general, tropospheric chemistry is analogous to a low-temperature
combustion system, the overall reaction is given by
CH
4
þ 2O
2
-CO
2
þ 2H
2
O (2.5)
Unlike combustion, this is not a thermally initiated process but a process
initiated and propagated by photochemistry. The chemistry that takes
place in the troposphere, and in particular, the photochemistry is
intrinsically linked to the chemistry of ozone. Tropospheric ozone acts
as initiator, reactant and product in much of the oxidation chemistry
that takes place in the troposphere and stratospheric ozone determines
the amount of short wavelength radiation available to initiate photo-
chemistry. Figure 6 shows a typical ozone profile through the atmos-
phere illustrating a number of interesting points. First, 90% of
atmospheric ozone can be found in the stratosphere (see Section 2.10);
on average about 10% can be found in the troposphere. Second, the
troposphere in the simplest sense consists of two regions. The lowest
kilometre or so contains the planetary boundary layer
6
and inversion
layers which can act as pre-concentrators for atmospheric emissions
from the surface and hinder exchange to the so-called free troposphere,
the larger part by volume, that sits above the boundary layer.
For a long time, transport from the stratosphere to the troposphere
was thought to be the dominant source of ozone in the troposphere.
7,8
Early in the 1970s, it was first suggested
9,10
that tropospheric ozone
originated mainly from production within the troposphere by photo-
chemical oxidation of CO and hydrocarbons catalysed by HO
x
and
NO
x
. These sources are balanced by in-situ photochemical destruction
of ozone and by dry deposition at the earth’s surface. Many studies,
both experimental- and model-based have set about determining the
17 Chemistry of the Atmosphere
contribution of both chemistry and transport to the tropospheric ozone
budget on many different spatial and temporal scales.
There is growing evidence that the composition of the troposphere is
changing.
11
For example, analysis of historical ozone records has indi-
cated that tropospheric ozone levels in both hemispheres have increased
by a factor of 3–4 over the last century. Methane concentrations have
effectively doubled over the past 150 years and N
2
O levels have risen by
15% since pre-industrial times.
12
Measurements of halocarbons have
shown that this group of chemically and radiatively important gases to
be increasing in concentration until relatively recently.
12
One of the difficulties about discussing tropospheric chemistry in
general terms is that by the very nature of the troposphere being the
lowest layer of the atmosphere it has complex multi-phase interactions
with the earth’s surface, which can vary considerably between expanses
of ocean to deserts (see Figure 7). The fate of any chemical species (C
i
) in
the atmosphere can be represented as a continuity or mass balance
equation such as
dC
i
dt
¼
duC
i
dx
À
dvC
i
dy
À
dwC
i
dz
þK
z
dC
i
dz
þP
i
ÀL
i
þS
i
þ
dC
i
dt

clouds
ð2:6Þ
Ozone concentration
Stratospheric
Ozone Ozone Layer
Ozone
increases
from pollution
Tropospheric
Ozone
A
l
t
i
t
u
d
e

(
k
i
l
o
m
e
t
e
r
s
)

A
l
t
i
t
u
d
e

(
m
i
l
e
s
)

35
30
25
20
15
10
5
0
20
15
10
5
Figure 6 A typical atmospheric ozone profile through the atmosphere.
58
The concentra-
tion is expressed as a volume mixing ratio
18 Chapter 2
F
i
g
u
r
e
7
A
s
c
h
e
m
a
t
i
c
r
e
p
r
e
s
e
n
t
a
t
i
o
n
o
f
t
h
e
a
t
m
o
s
p
h
e
r
e

s
r
o
l
e
i
n
t
h
e
e
a
r
t
h
s
y
s
t
e
m
19 Chemistry of the Atmosphere
where t is the time, u, v and w are the components of the wind vector in
x, y and z accounting for the horizontal and vertical large-scale trans-
port. Small-scale turbulence can be accounted for using K
z
, the turbulent
diffusion coefficient, P
i
and L
i
are the chemical production and loss
terms and S
i
are the sources owing to emissions. Cloud processes
(vertical transport, washout and aqueous phase chemistry) are repre-
sented in a cloud processing term. The application of this type of
equation is the basis of chemical modelling. In this chapter we will
concentrate mainly on the chemical terms in this equation and the
processes that control them, but inherently, as the study of tropospheric
photochemistry is driven by observations, these must be placed within
the framework of Equation (2.6).
2.5 TROPOSPHERIC OXIDATION CHEMISTRY
Though atmospheric composition is dominated by both oxygen and
nitrogen, it is not the amount of oxygen that defines the capacity of the
troposphere to oxidise a trace gas. The ‘‘oxidising capacity’’ of the
troposphere is a somewhat nebulous term probably best described by
Thompson.
13
The total atmospheric burden of O
3
, OH and H
2
O
2
determines the
‘‘oxidising capacity’’ of the atmosphere. As a result of the multiple
interactions among the three oxidants and the multiphase activity of
H
2
O
2
, there is no single expression that defines the earth’s oxidising
capacity. Some researchers take the term to mean the total global OH,
although even this parameter is not defined unambiguously.
Figure 8 gives a schematic representation of tropospheric chemistry,
representing the links between emissions, chemical transformation and
sinks for a range of trace gases.
Atmospheric photochemistry produces a variety of radicals that exert
a substantial influence on the ultimate composition of the atmosphere.
14
Probably the most important of these in terms of its reactivity is the
hydroxyl radical, OH. The formation of OH is the initiator of radical-
chain oxidation. Photolysis of ozone by UV light in the presence of water
vapour is the main source of hydroxyl radicals in the troposphere, viz
O
3
þ hn(l o 340 nm) -O(
1
D) þ O
2
(
1
D
g
) (2.7)
O(
1
D) þ H
2
O -OH þ OH (2.8)
20 Chapter 2
The fate of the bulk of the O(
1
D) atoms produced via reaction (2.7) is
collisional quenching back to ground-state oxygen atoms, viz
O(
1
D) þ N
2
-O(
3
P) þ N
2
(2.9)
O(
1
D) þ O
2
-O(
3
P) þ O
2
(2.10)
The fraction of O(
1
D) atoms that form OH is dependent on pressure and
the concentration of H
2
O; typically in the marine boundary layer (MBL)
about 10% of the O(
1
D) generate OH. Reactions (2.7 and 2.8) are the
primary source of OH in the troposphere, but there are a number of
other reactions and photolysis routes capable of forming OH directly or
indirectly. As these compounds are often products of OH radical initi-
ated oxidation they are often termed secondary sources of OH and
include the photolysis of HONO, HCHO, H
2
O
2
and acetone and the
reaction of O(
1
D) with methane (see Figure 9). Table 2 illustrates the
average contribution of various formation routes with altitude in a
standard atmosphere.
Two important features of OH chemistry make it critical to the chem-
istry of the troposphere. The first is its inherent reactivity; the second is its
Figure 8 A simplified scheme of tropospheric chemistry. The figure illustrates the
interconnections in the chemistry, as well as the role of sources, chemical
transformation and sinks
21 Chemistry of the Atmosphere
relatively high concentration given its high reactivity. The hydroxyl
radical is ubiquitous throughout the troposphere owing to the widespread
nature of ozone and water. In relatively unpolluted regimes (low NO
x
) the
main fate for the hydroxyl radical is reaction with either carbon monoxide
or methane to produce peroxy radicals such as HO
2
and CH
3
O
2
, viz
OH þ CO -H þ CO
2
(2.11)
H þ O
2
þ M -HO
2
þ M (2.12)
P L
LOSS
RADICAL - RADICAL
HO
2
+ HO
2
HO
2
+ RO
2
RO
2
+ RO
2
RADICAL - NO
x
OH + NO
2
HO
2
+ NO
2
RO + NO → Nitrate
RCO
3
+ NO
2
Heterogeneous
PRODUCTION
j(O
1
D)
j(HONO)
j(HCHO)
j(H
2
O
2
)
O
3
+ C
n
H
2n
j(ROOH)
j(RCHO)
j(H
2
O)
RO
2
CH
4
, HC
CO
HO
2 OH
NO, O
3
NO
Figure 9 The sources, interconversions and sinks for HO
x
(and ROx) in the tropo-
sphere
14
Table 2 Calculated fractional contribution of various photolysis rates to radical
production with altitude
Altitude
j(O(
1
D)) þ
H
2
O
j(O(
1
D)) þ
CH
4
j(Acetone) j(H
2
O
2
) j(HCHO)
Ground 0.68 0.0 Neg. 0.15 0.17
Mid-
troposphere
0.52 Neg. 0.03 0.20 0.25
Upper-
troposphere
0.35 0.02 0.1 0.25 0.28
Lower
stratosphere
0.40 0.1 0.25 0.1 0.15
Note: (Neg: Negligible).
22 Chapter 2
and
OH þ CH
4
-CH
3
þ H
2
O (2.13)
CH
3
þ O
2
þ M-CH
3
O
2
þ M (2.14)
In low-NO
x
conditions, HO
2
can react with ozone leading to further
destruction of ozone in a chain sequence involving production of
hydroxyl radicals.
HO
2
þ O
3
-OH þ 2O
2
(2.15)
OH þ O
3
-HO
2
þ O
2
(2.16)
Alternatively, it can recombine to form hydrogen peroxide (H
2
O
2
)
HO
2
þ HO
2
-H
2
O
2
þ O
2
(2.17)
or react with organic peroxy radicals such as CH
3
O
2
to form organic
hydroperoxides,
CH
3
O
2
þ HO
2
-CH
3
O
2
H þ O
2
(2.18)
The formation of peroxides is effectively a chain termination reaction, as
under most conditions these peroxides can act as effective sinks for HO
x
.
In more polluted conditions (high-NO
x
), peroxy radicals catalyse the
oxidation of NO to NO
2
HO
2
þ NO -OH þ NO
2
(2.19)
leading to the production of ozone from the subsequent photolysis of
nitrogen dioxide and reaction of the photoproducts, i.e.
NO
2
þ hn(l o 420 nm) -NO þ O(
3
P) (2.2)
O þ O
2
þ M -O
3
þ M (2.20)
Hydroxyl radicals produced in reaction (2.19) can go on to form more
peroxy radicals (e.g. via reactions (2.11) and (2.13)). Similarly to HO
2
,
CH
3
O
2
can also oxidise NO to NO
2
.
CH
3
O
2
þ NO -CH
3
O þ NO
2
(2.21)
23 Chemistry of the Atmosphere
The resulting methoxy radical reacts rapidly with O
2
to form formalde-
hyde and HO
2
.
CH
3
O þ O
2
-HCHO þ HO
2
(2.22)
The oxidation of methane is summarised schematically in Figure 10. The
OH radical may have another fate, dependant on the concentration of
NO
2
, it can react with NO
2
to form nitric acid.
OH þ NO
2
þ M -HNO
3
þ M (2.23)
The formation of HNO
3
represents an effective loss mechanism for both
HO
x
and NO
x
.
CH
3
OOH
HO
2
CH
3
O
2
NO
NO
2
CH
3
O
O
3
O
2
O
3
HO
2
NO
NO
2
OH
O
3
hν + O
2
hν + O
2
HCHO

CO(+2HO
2
)
CH
3
CH
4
+
OH O
3
+ hν
H
2
O
+ O
2

+ O
2
CO
2
Figure 10 Simplified mechanism for the photochemical oxidation of CH
4
in the troposphere
62
24 Chapter 2
Example lifetime calculation
For the reaction, CH
4
þOH-CH
3
þH
2
O that is the key loss process
for CH
4
(a greenhouse gas), the rate coefficient for the reaction at
atmospheric temperatures is given by k ¼ 8.4 Â 10
À15
cm
3
molecule
À1
s
À1
. Given the mean atmospheric concentration is [OH] ¼ 5 Â 10
5
molecule cm
À3
, what is the atmospheric lifetime of CH
4
?
Answer: For a reaction of the type A þ B -P (i.e. second-order) the
atmospheric lifetime is given by
t
CH
4
OH
¼
1
k½OHŠ
¼
1
ð6:3 Â10
À15
Þð5 Â10
5
Þ
¼ 3:1 Â10
8
s ¼ 9:9 years
The type of calculations are useful as they give an indication of the
likely chemical lifetime (i.e. the amount of time it will take before a
molecule is reacted away) of a molecule in the atmosphere. Clearly,
this form of calculation does not take into account any other chemical
loss routes other than reaction with OH or any other physical process
that may remove a molecule.
Temperature dependence of a reaction
The lifetime of a compound in the atmosphere will depend on how
fast it reacts with main atmospheric oxidants. Many reaction rates
vary with temperature, therefore in the atmosphere the lifetime will
vary with altitude. For the reaction between OH and CH
4
, the
temperature dependence of the reaction is given by k ¼ 1.85 Â
10
À12
exp(À1690/T). How does the reaction rate vary between 0.1
and 10 km and therefore effect the lifetime? For the lifetime calcula-
tion see previous description.
Answer:
Region
Altitude
(km) T (1C)
k (cm
3
molecule
À1
s
À1
)
t
OH
(years)
Boundary layer 0.1 25 6.3 Â 10
À15
9.9
Lower troposphere 1 9 4.6 Â 10
À15
13.8
Middle troposphere 6 À24 2.0 Â 10
À15
30.3
Lower stratosphere 10 À56 7.6 Â 10
À16
82.7
25 Chemistry of the Atmosphere
2.5.1 Nitrogen Oxides and the Photostationary State
From the preceding discussion, it can be seen that the chemistry of
nitrogen oxides are an integral part of tropospheric oxidation and
photochemical processes. Nitrogen oxides are released into the tropo-
sphere from a variety of biogenic and anthropogenic sources including
fossil fuel combustion, biomass burning, microbial activity in soils and
lightning discharges (see Figure 2). About 30% of the global budget of
NO
x
, i.e. (NO þ NO
2
) comes from fossil fuel combustion with almost
86% of the NO
x
emitted in one form or the other into the planetary
boundary layer from surface processes.
5
Typical NO/NO
2
ratios in
surface air are 0.2–0.5 during the day tending to zero at night. Over
the timescales of hours to days NO
x
is converted to nitric acid (reaction
(2.23)) and nitrates, which are subsequently removed by rain and dry
deposition.
The photolysis of NO
2
to NO and the subsequent regeneration of NO
2
via reaction of NO with ozone is sufficiently fast, in the moderately
polluted environment, for these species to be in dynamic equilibrium, viz
NO
2
þ hn -NO þ O(
3
P) (2.2)
O(
3
P) þ O
2
þ M -O
3
þ M (2.20)
O
3
þ NO -NO
2
þ O
2
(2.24)
Therefore, at suitable concentrations, ambient NO, NO
2
and O
3
can be
said to be in a photochemical steady-state or photostationary state
(PSS),
15
provided that they are isolated from local sources of NO
x
and
that sunlight intensity is relatively constant, therefore
½O
3
Š ¼
j
2:2
½NO
2
Š
k
2:24
½NOŠ
ð2:25Þ
The reactions (2.2, 2.20 and 2.24) constitute a cycle with no net chem-
istry. The PSS expression is sometimes expressed as a ratio, viz
f ¼
j
2:2
½NO
2
Š
k
2:24
½NOŠ½O
3
Š
ð2:26Þ
If ozone is the sole oxidant for NO to NO
2
then f ¼ 1. This situation
often pertains in urban areas where NO
x
levels are high and other
potential oxidants of NO to NO
2
such as peroxy radicals are suppressed.
In the presence of peroxy radicals, Equation (2.25) has to be modified as
26 Chapter 2
the NO/NO
2
partitioning is shifted to favour NO
2
, viz
½NO
2
Š
½NOŠ
¼ ðk
2:24
½O
3
Š þk
2:19
½HO
2
Š þk
2:21
½RO
2
ŠÞ=j
2:2
ð2:27Þ
Though the radical concentrations are typically ca. 1000 times smaller
than the [O
3
], the rate of the radical oxidation of NO to NO
2
is ca. 500
times larger than the corresponding oxidation by reaction with O
3
. We
shall return to the significance of the peroxy radical catalysed oxidation
of NO to NO
2
when considering photochemical ozone production and
destruction. From the preceding discussion, it can be seen that the
behaviour of NO and NO
2
are strongly coupled through both photolytic
and chemical equilibria. Because of their rapid interconversion they are
often referred to as NO
x
. NO
x
, i.e. (NO þ NO
2
) is also sometimes
referred to as ‘‘active nitrogen’’.
Photostationary state
At what NO
2
/NO ratio will the PSS ratio be equal to 1 for midday
conditions (j
2.2
¼ 1 Â 10
À3
s
À1
) given that k
2.24
¼ 1.7 Â 10
À14
cm
3
molecule
À1
s
À1
and that O
3
¼ 30 ppbv.
Using the Equation (2.26)
f ¼
j
2:2
½NO
2
Š
k
2:24
½NOŠ½O
3
Š
Converting O
3
from ppbv to molecule cm
À3
, as 1 ppbv ¼ 2.46 Â 10
10
molecule cm
À3
(at 251C and 1 atm) 30 ppbv ¼ 7.38 Â 10
11
molecule
cm
À3
. Given that f ¼ 1 then
½NO
2
Š
½NOŠ
¼
k
2:24
½O
3
Š
j
2:2
[NO
2
]/[NO] ¼ 12.55
The extent of the influence of NO
x
in any given atmospheric situation
depends on its sources, reservoir species and sinks. Therefore, an
important atmospheric quantity is the lifetime of NO
x
. If nitric acid
formation is considered to be the main loss process for NO
x
(i.e. NO
2
),
then the lifetime of NO
x
(t
NO
x
) can be expressed as the time constant for
reaction (2.23), the NO
2
to HNO
3
conversion.
t
NO
x
¼
1
k
2:23
½OHŠ
1 þ
½NOŠ
½NO
2
Š

ð2:28Þ
27 Chemistry of the Atmosphere
Therefore, using this simplification, the lifetime of NO
x
is dependent on the
[OH] and [NO]/[NO
2
] ratio. Calculating t
NO
x
under typical upper tropo-
spheric conditions gives lifetimes in the order of 4–7 days and lifetimes in
the order of days in the lower free troposphere. In the boundary layer, the
situation is more complex as there are other NO
x
loss and transformation
processes other than those considered in Equation (2.29), which can make
t
NO
x
as short as 1 h. Integrally linked to the lifetime of NO
x
and therefore
the role of nitrogen oxides in the troposphere is its relation to odd nitrogen
reservoir species, i.e. NO
y
. The sum of total reactive nitrogen or total odd
nitrogen is often referred to as NO
y
and can be defined as NO
y
¼ NO
x
þ
NO
3
þ 2N
2
O
5
þ HNO
3
þ HNO
4
þ HONO þ PAN þ nitrate aerosol þ
alkyl nitrate, where PAN is peroxyacetlynitrate (see Section 2.5.4). NO
y
can
also be thought of as NO
x
plus all the compounds that are products of the
atmospheric oxidation of NO
x
. NO
y
is not a conserved quantity in the
atmosphere owing to the potential for some of its constituents (e.g. HNO
3
)
to be efficiently removed by deposition processes. Mixing of air masses may
also lead to dilution of NO
y
. The concept of NO
y
is useful in considering
the budget of odd nitrogen and evaluating the partitioning of NO
x
and its
reservoirs in the troposphere.
16
In summary, the concentration of NO
x
in the troposphere
determines the catalytic efficiency of ozone production;
determines the partitioning of OH and HO
2
;
determines the amount of HNO
3
and nitrates produced; and
determines the magnitude and sign of net photochemical produc-
tion or destruction of ozone (see Section 2.5.2).
2.5.2 Production and Destruction of Ozone
From the preceding discussion of atmospheric photochemistry and NO
x
chemistry, it can be seen that the fate of the peroxy radicals can have a
marked effect on the ability of the atmosphere either to produce or to
destroy ozone. Photolysis of NO
2
and the subsequent reaction of the
photoproducts with O
2
(reactions (2.4) and (2.20)) are the only known
way of producing ozone in the troposphere. In the presence of NO
x
the
following cycle for the production of ozone can take place:
NO
2
þ hn -O(
3
P) þ NO (2.2)
O(
3
P) þ O
2
þ M -O
3
þ M (2.20)
OH þ CO -H þ CO
2
(2.11)
28 Chapter 2
H þ O
2
þ M -HO
2
þ M (2.12)
HO
2
þ NO -OH þ NO
2
(2.19)
NET: CO þ 2O
2
þ hn -CO
2
þ O
3
(2.29)
Similar chain reactions can be written for reactions involving RO
2
. In
contrast, when relatively little NO
x
is present, as in the remote atmos-
phere, the following cycle can dominate over ozone production leading
to the catalytic destruction of ozone, viz
HO
2
þ O
3
-OH þ 2O
2
(2.15)
OH þ CO -H þ CO
2
(2.11)
H þ O
2
þ M -HO
2
þ M (2.12)
NET: CO þ O
3
-CO
2
þ O
2
(2.30)
Clearly, there is a balance between photochemical ozone production and
ozone loss dependent on the concentrations of HO
x
and NO
x
. Figure 11
shows the dependence of the production of ozone on NO
x
taken from a
numerical model. There are distinct regions in terms of N(O
3
) vs. [NO
x
]
A
B
C
8
6
4
2
0
-2
1 10 100 1000
NOx (pptv)
n
e
t

o
z
o
n
e

p
r
o
d
u
c
t
i
o
n

(
p
p
b
v

d
a
y
-
1
)
Figure 11 Schematic representation of the dependence of the net ozone (N(O
3
))
production (or destruction) on the concentration of NO
x
29 Chemistry of the Atmosphere
on Figure 11. For example, in region A the loss of ozone (L(O
3
)) is
greater than the production of ozone (P(O
3
)), hence the net product of
this process, i.e.
N(O
3
) ¼ P(O
3
) À L(O
3
) (2.31)
leads to a net ozone loss. The photochemical loss of ozone can be
represented as
L(O
3
) ¼ (f Á j
2.7
(O
1
D) Á [O
3
]) þ k
2.15
[HO
2
] þ k
2.16
[OH] (2.32)
where f is the fraction of O(
1
D) atoms that react with water vapour
(reaction (2.8)) rather than are deactivated to O(
3
P) (reactions (2.9) and
(2.10)). Evaluation of Equation (2.32) is effectively a lower limit for the
ozone loss rate as it neglects any other potential chemical loss processes
for ozone such as cloud chemistry,
17
NO
3
chemistry (see Section 2.6) or
halogen chemistry (see Section 2.9). The balance point, i.e. where N(O
3
)
¼ 0 is often referred to, somewhat misleadingly, as the compensation
point and occurs at a critical concentration of NO
x
. Above the com-
pensation point P(O
3
)4L(O
3
) and therefore N(O
3
) is positive and the
system is forming ozone. The in-situ formation rate for ozone is ap-
proximately given by the rate at which the peroxy radicals (HO
2
and
RO
2
) oxidise NO to NO
2
. This is followed by the rapid photolysis of
NO
2
(reaction (2.4)) to yield the oxygen atom required to produce O
3
.
P(O
3
) ¼ [NO] Á (k
2.19
[HO
2
] þ Sk
i
[RO
2
]
i
) (2.33)
It is also worth noting that P(O
3
) can also be expressed in terms of the
concentrations of NO
x
, j
2.2
(NO
2
), O
3
and temperature by substitution of
Equation (2.27) into Equation (2.33) to give
P(O
3
) ¼ j
2.2
[NO
2
] À k
2.24
[NO][O
3
] (2.34)
At some concentration of NO
x
the system reaches a maximum produc-
tion rate for ozone at dP(O
3
)/d(NO
x
) ¼ 0 and even though P(O
3
) is still
significantly larger than L(O
3
) the net production rate begins to fall off
with increasing NO
x
. Until this maximum is reached the system is said to
be NO
x
limited with respect to the production of ozone. The turn-over,
i.e. dP(O
3
)/d(NO
x
) ¼ 0 is caused by the increased competition for NO
x
by the reaction
OH þ NO
2
þ M -HNO
3
þ M (2.23)
In reality, the situation is somewhat more complicated owing to the
presence at high concentrations of NO
x
of increased levels of non-
methane hydrocarbons (NMHCs), especially in places such as the urban
30 Chapter 2
atmosphere. The oxidation of NMHCs in common with much of tropo-
spheric oxidation chemistry, is initiated by reaction with OH, leading to
the rapid sequence of chain reactions.
OH þ RH -R þ H
2
O (2.35)
R þ O
2
þ M -RO
2
þ M (2.36)
RO
2
þ NO -RO þ NO
2
(2.37)
RO -carbonyl products þ HO
2
(2.38)
HO
2
þ NO -OH þ NO
2
(2.19)
This cycle is similar to the preceding one for the oxidation of CO, in that
it is catalytic with respect to OH, R, RO and RO
2
, with HO
2
acting as
the chain propagating radical. The mechanism of reaction (2.38) is
strongly dependent on the structure of RO.
Photochemical production of ozone
Calculate the photochemical production rate of ozone at midday,
given that j
2.2
¼ 1 Â 10
À3
s
À1
, O
3
¼ 30 ppbv and k
2.24
¼ 1.7 Â 10
À14
cm
3
molecule
À1
s
À1
for a 2:1 ratio of NO
2
/NO.
Using the equation
P(O
3
) ¼ j
2.2
[NO
2
] À k
2.24
[NO][O
3
]
As the rate constant is in the units of cm
3
molecule
À1
s
À1
, all the
concentrations should be converted into molecule cm
À3
(as per PSS
example). The answer should be converted into ppb h
À1
by dividing
the answer in cm
3
molecule
À1
s
À1
into ppbv and turning the seconds
into hours. For NO
2
¼ 2 ppbv, NO ¼ 1 ppbv, P(O
3
) ¼ 7.1 ppbv h
À1
.
The equation scales as per the absolute values of NO
2
/NO used.
With the involvement of volatile organic compounds (VOCs) in the
oxidation chemistry, Figure 11 represents a slice through an n-dimen-
sional surface where there should be a third axis to represent the
concentration of VOCs. The peak initial concentrations of ozone gen-
erated from various initial concentrations of NO
x
and VOCs are usually
represented as an ‘‘O
3
isopleth diagram’’, an example of which is shown
31 Chemistry of the Atmosphere
in Figure 12.
18
In an isopleth diagram, initial mixture compositions
giving rise to the same peak O
3
concentration are connected by the
appropriate isopleth. An isopleth plot shows that ozone production is a
highly non-linear process in relation to NO
x
and VOC, but picks out
many of the features already highlighted in Figure 11, i.e. when NO
x
is
‘‘low’’ the rate of ozone formation increases with increasing NO
x
in a
near-linear fashion. On the isopleth, the local maximum in the ozone
formation rate with respect to NO
x
is the same feature as the turn over
in N(O
3
) in Figure 11. The ridgeline along the local maximum separates
two different regimes, the so-called NO
x
-sensitive regime, i.e. N(O
3
) p
(NO
x
) and the VOC-sensitive (or NO
x
saturated regime), i.e. N(O
3
) p
(VOC) and increases with increasing NO
x
. The relationship between
NO
x
, VOCs and ozone embodied in the isopleth diagram indicates one
of the problems in the development of air quality policy with respect to
ozone. Reductions in VOC are only effective in reducing ozone under
VOC-sensitive chemistry (high NO
x
) and reductions in NO
x
will only be
effective if NO
x
-sensitive chemistry predominates and may actually
increase ozone in VOC-sensitive regions. In general, as an air mass
moves away from emission sources, e.g. in an urban region, the chem-
istry tends to move from VOC-sensitive to NO
x
-sensitive chemistry.
10 100 1000
5
10
20
100
50
20
10
5
2
1
VOC (ppbC)
N
O
x

(
p
p
b
v
)
1
2
Figure 12 Isopleths giving net rate of ozone production (ppb h
À1
) as a function of VOC
(ppbC) and NO
x
(ppbv) for mean summer daytime meteorology and clear
skies
18
32 Chapter 2
Case Study I – A practical example of the dependence of ozone
production on NO
x
– An example of the experimental determination
of these relationships is shown in Figure 13, a comparison of observed
ozone production rates (P(O
3
)) and concentrations of HO
2
and OH
from the NASA SONEX mission
19
plotted as a function of NO
x
. The
data were taken from a suite of aircraft measurements between 8 and
12 km altitude at latitudes between 40 and 601N. The model data
suggest that P(O
3
) becomes independent of NO
x
above 70 pptv and
the turn-over point into a NO
x
-saturated regime occurs at about 300
pptv. The bulk of the experimental observation below [NO
x
] o 300
1
3
2
1
0
(a)
(b)
(c)
2
1
0
0.15
0.10
0.05
0.00
10 100 1000
NO
x
(pptv)
O
H

(
p
p
t
v
)
H
O
2

(
p
p
t
v
)
P
(
O
3
)

(
p
p
b
v

d
a
y
-
1
)
Figure 13 Observed ozone production rates (P(O
3
)) and concentrations of HO
2
and OH
during SONEX (8–12 km altitude, 40–601N latitude) plotted a function of the
NO
x
concentration (NO
x
¼ observed NO þ modelled NO
2
). The observed
rates and concentrations are averaged over 24 h, using diel factors obtained
from a locally constrained box model. The lines on the three panels correspond
to model-calculated values for median upper tropospheric conditions as en-
countered during SONEX
19
33 Chemistry of the Atmosphere
pptv observe the P(O
3
) dependency predicted by the model, but above
[NO
x
] B300 pptv P(O
3
), computed from the measured HO
2
and NO,
continues to increase with NO
x
, suggesting a NO
x
-limited regime.
Case Study II – Photochemical control of ozone in the remote marine
boundary layer (MBL) – An elegant piece of experimental evidence for
the photochemical destruction of ozone comes from studies in the
remote MBL over the southern ocean at Cape Grim, Tasmania
(411S).
20
In the MBL, the photochemical processes are coupled to
physical processes that affect the observed ozone concentrations,
namely deposition to the available surfaces and entrainment from
the free troposphere. The sum of these processes can be represented in
the form of an ozone continuity equation (a simplified version of
Equation 2.6), viz
d½O
3
Š
dt
¼ C þ
E
v
ð½O
3
Š
ft
À½O
3
ŠÞ
H
þ
v
d
½O
3
Š
H
ð2:39Þ
where C is a term representative of the photochemistry (the net result
of production, P(O
3
), minus destruction, L(O
3
) Equation (2.32)), E
v
the entrainment velocity (a measure of the rate of ozone transport
into the boundary layer), [O
3
]
ft
the concentration of free-tropospheric
ozone, v
d
the dry deposition velocity (a measure of the physical loss of
ozone to a surface) and H the height of the boundary layer. In
general, the MBL is particularly suitable for making photochemical
measurements owing to its stable and chemically simple nature.
Figure 14 shows the average diurnal cycle of ozone and total peroxide
(mainly H
2
O
2
) in clean oceanic air as measured at Cape Grim during
January 1992. During the sunlit hours an ozone loss of about 1.6
ppbv occurs between mid-morning and late afternoon. This loss of
ozone is followed by an overnight replenishment to a similar starting
point. In contrast, the peroxide concentration decreases overnight
from 900 to 600 pptv and then increases from 600 to 900 pptv between
midmorning and late afternoon. It is worth noting that the magnitude
of this anti-correlation of ozone and peroxide is dependent on season.
The daytime anti-correlation between O
3
and peroxide can be inter-
preted as experimental evidence for the photochemical destruction of
ozone, as the ozone is destroyed via reactions (2.7, 2.15 and 2.16)
while simultaneously peroxide is formed from chemistry involving the
odd-hydrogen radicals OH and HO
2
(reactions (2.11, 2.12 and 2.17)).
34 Chapter 2
The night-time replenishment of ozone is caused by entrainment of
ozone from the free troposphere into the boundary layer. The over-
night loss of peroxide is due to deposition over the sea surface (and
heterogeneous loss to the aerosol surface), as peroxide has a signif-
icant physical loss rate, in contrast to ozone which does not. There-
fore, the daytime anti-correlation of ozone and peroxide is indicative
of the net photochemical destruction of ozone.
2.5.3 Role of Hydrocarbons
The discussion up to this point has focused in the main on the role of CO
and CH
4
as the fuels for atmospheric oxidation. It is clear that there are
many more carbon compounds in the atmosphere than just these two.
21
One of the roles of atmospheric photochemistry is to ‘‘cleanse’’ the
troposphere of a wide-range of these compounds. Table 3 illustrates the
global turnover of a range of trace gases including hydrocarbons and
illustrates, for a number of trace gases, the primary role played by OH in
their removal. NMHC have a range of both biogenic and anthropogenic
sources.
5,21
Carbon monoxide chemistry is not independent from
NMHC chemistry as 40–60% of surface CO levels over the continents,
slightly less over the oceans, and 30–60% of CO levels in the free
troposphere, are estimated to come from NMHC oxidation.
22
15.0
14.8
14.6
14.4
14.2
14.0
13.8
13.6
13.4
13.2
13.0
1,100
1,000
900
800
700
600
500
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

p
e
r
o
x
i
d
e
s

(
p
p
t
v
)
C
o
n
c
e
n
t
r
a
t
i
o
n


o
f

o
z
o
n
e

(
p
p
b
v
)
1 6 12 18 21
Hour of day
Figure 14 Average diurnal cycles for peroxide (open squares) and ozone (filled squares)
in baseline air at Cape Grim, Tasmania (411S) for January 1992
20
35 Chemistry of the Atmosphere
A major component of the reactive hydrocarbon loading are the
biogenic hydrocarbons.
21
As previously indicated, the hydrocarbon
oxidation chemistry is integral to the production of ozone. Globally,
the contribution of NMHC to net photochemical production of ozone is
estimated to be about 40%.
23
There are a number of inorganic molecules such as NO
2
and SO
2
(See
Table 3) which are also lost via reaction with OH. A number of
halocarbons also exist that posses insubstantial tropospheric sinks and
have importance in the chemistry of the stratosphere (see Section 2.10).
The ultimate products of the oxidation of any hydrocarbon are
carbon dioxide and water vapour, but there are many relatively stable
partially oxidised organic species such as aldehydes, ketones and carbon
monoxide that are produced as intermediate products during this proc-
ess, with ozone produced as a by-product of the oxidation process.
Figure 10 shows a schematic representation of the free radical catalysed
oxidation of methane, which is analogous to that of a hydrocarbon. As
previously discussed, the oxidation is initiated by reaction of the hydro-
carbon with OH and follows a mechanism in with the alkoxy and peroxy
radicals are chain propagators and OH is effectively catalytic, viz
OH þ RH -R þ H
2
O (2.35)
R þ O
2
þ M -RO
2
þ M (2.36)
RO
2
þ NO -RO þ NO
2
(2.37)
RO -carbonyl products þ HO
2
(2.38)
Table 3 Global turnover of tropospheric gases and fraction removed by reaction
with OH
Trace gas Global emission rate(Tg yr
À1
) Removal by OH
a
(%)
CO 2800 85
CH
4
530 90
C
2
H
6
20 90
Isoprene 570 90
Terpenes 140 50
NO
2
150 50
SO
2
300 30
(CH
3
)
2
S 30 90
CFCl
3
0.3 0
a
Assuming mean global [OH] ¼ 1 Â 10
6
molecule cm
À3
.
Source: After ref. 59.
36 Chapter 2
HO
2
þ NO -OH þ NO
2
(2.19)
As both reactions (2.37) and (2.19) lead to the oxidation of NO to NO
2
the subsequent photolysis leads to the formation of ozone (see reactions
(2.2) and (2.20)). The individual reaction mechanism depends on the
identity of the organic compounds and the level of complexity of the
mechanism. Although OH is the main tropospheric oxidation initiator,
reaction with NO
3
, O
3
, O(
3
P) or photolysis may be an important loss
route for some NMHCs or the partially oxygenated products produced
as intermediates in the oxidation (see reaction (2.38)).
In summary, the rate of oxidation of VOCs and therefore by inference
the production of ozone is governed by the concentration of the catalytic
HO
x
radicals. There are a large variety of VOCs with a range of
reactivities; therefore this remains a complex area.
2.5.4 Urban Chemistry
In some respects, the story of atmospheric chemistry and particularly ozone
photochemistry begins with urban chemistry and photochemical smog. The
term smog arises from a combination of the words smoke and fog. In the
1940s, it became apparent that cities like Los Angeles (LA) were severely
afflicted with a noxious haze.
24
Though, at the time it was thought to be a
relatively local phenomenon, with the understanding of its chemistry came
the development of a photochemical theory for the whole of the tropo-
sphere. The LA smog is often termed photochemical smog and is quite
different in origin to the London smogs of the 19th and 20th centuries,
which have their origins in abnormally high concentrations of smoke
particles and sulfur dioxide. The London smogs have been alleviated with
the effective application of legislation that has reduced the burning of coal
in the London area. The major features of photochemical smog are high
levels of oxidant concentration in particular ozone and peroxidic com-
pounds, produced by photochemical reactions. The principal effects of
smog are eye and bronchial irritation as well as plant and material damage.
The basic reaction scheme for the formation of photochemical smog is
VOC þ hn -VOC þ R (2.40)
R þ NO -NO
2
(2.41)
NO
2
þ hn(l o 420 mm) -NO þ O
3
(2.2)
37 Chemistry of the Atmosphere
NO þ O
3
-NO
2
þ O
2
(2.24)
R þ R -R (2.42)
R þ NO
2
-NO
y
(2.43)
There is a large range of available VOCs in the urban atmosphere,
driven by the range of anthropogenic and biogenic sources.
5,21,31
Table 4
illustrates the different loadings of the major classes of NMHC in urban
and rural locations. These NMHC loadings must be coupled to meas-
ures of reactivity and the degradation mechanisms of the NMHC to give
a representative picture of urban photochemistry. The oxidation of the
VOCs drives, via the formation of peroxy radicals, the oxidation of NO
to NO
2
, where under the sunlit conditions the NO
2
can be dissociated to
form ozone (reaction (2.2)). Pre-existing ozone can also drive the NO to
NO
2
conversion (reaction (2.24)).
The basic chemistry responsible for urban photochemistry is essen-
tially the same as that takes place in the unpolluted atmosphere (see
Section 2.5). It is the range and concentrations of NMHC fuels and the
concentrations of NO
x
coupled to the addition of some photochemical
accelerants that can lead to the excesses of urban chemistry. For
example, in the Los Angeles basin it is estimated that 3333 ton day
À1
of organic compounds are emitted as well as 890 ton day
À1
of NO
x
. In
addition, to the reactions forming OH in the background troposphere,
i.e. via the reaction of O(
1
D) with H
2
O, viz
O
3
þ hn(l o 340 nm) -O
2
þ O(
1
D) (2.7)
O(
1
D) þ H
2
O -2OH (2.8)
Table 4 Percentage of NMHC classes measured in the morning at various
locations
Urban Los Angeles Urban Boston Rural Alabama
Alkanes 42 36 9
Alkenes 7 10 43
a
Aromatics 19 30 2
Other 33 24 46
b
Source: From ref. 31.
a
Large contribution from biogenic alkenes.
b
Mainly oxygen containing.
38 Chapter 2
under urban conditions OH may be formed from secondary sources
such as
HONO þ hn(l o 400 nm) -OH þ NO (2.44)
where the HONO can be emitted in small quantities from automobiles
or formed from a number of heterogeneous pathways,
25
as well as gas-
phase routes. OH produced from HONO has been shown to be the
dominant OH source in the morning under some urban conditions,
where the HONO has built up to significant levels overnight. Another
key urban source of OH can come from the photolysis of the aldehydes
and ketones produced in the NMHC oxidation chemistry, in particular
formaldehyde, viz.
HCHO þ hn(l o 334 nm) -H þ HCO (2.45)
H þ O
2
þ M -HO
2
þ M (2.12)
HCO þ O
2
-HO
2
þ CO (2.46)
Net
HCHO þ 2O
2
þ hn -2HO
2
þ CO (2.47)
Smog chamber experiments have shown that the addition of aldehyde
significantly increases the formation rates of ozone and the conversion
rates of NO and NO
2
under simulated urban conditions.
3
A marked by-product of oxidation in the urban atmosphere, often
associated, but not exclusive to, urban air pollution is PAN. PAN is
formed by
OH þ CH
3
CHO -CH
3
CO þ H
2
O (2.48)
CH
3
CO þ O
2
-CH
2
CO
d
O
2
(2.49)
addition of NO
2
to the peroxyacetyl radical (RCO
d
O
2
) leading to the
formation of PAN.
CH
3
CO
d
O
2
þ NO
2
þ M "CH
3
CO
d
O
2
d
NO
2
þ M (2.50)
PAN is often used as an unambiguous marker for tropospheric chem-
istry. The lifetime of PAN in the troposphere is very much dependant on
the temperature dependence of the equilibrium in reaction (2.50), the
lifetime varying from 30 min at T ¼ 298 K to 8 h at T ¼ 273 K. At mid-
troposphere temperature and pressures PAN has thermal decomposition
39 Chemistry of the Atmosphere
lifetimes in the order of 46 days. It is also worth noting that peroxyacyl
radical like peroxy radicals can oxidise NO to NO
2
CH
3
CO
d
O
2
þ NO -CH
3
CO
d
O þ NO
2
(2.51)
PAN can be an important component of NO
y
in the troposphere (see
Section 2.5.1) and has the potential to act as a temporary reservoir for
NO
x
and in particular it has the potential to transport NO
x
from
polluted regions into the background/remote atmosphere.
26
There are other side-products of urban air pollution that are giving
increasing cause for concern. These include the production of both
aerosols (both organic and inorganic) and particles.
The effects of photochemical smog/urban air pollution remain on the
political agenda owing to their potential impact on human health and
the economy. In summary, urban photochemistry is not substantially
different from tropospheric photochemistry. It is the range and concen-
trations of the VOCs involved in oxidation coupled to the concentration
of NO
x
and other oxidants that lead to a large photochemical turnover.
2.6 NIGHT-TIME OXIDATION CHEMISTRY
Though photochemistry does not take place at night, it is important to
note, within the context of tropospheric oxidation chemistry, the potential
for oxidation chemistry to continue at night. This chemistry does not lead
to the production of ozone, in fact the opposite, but has importance
owing to the potential for the production of secondary pollutants. In the
troposphere, the main night-time oxidant is thought to be the nitrate
radical formed by the relatively slow oxidation of NO
2
by O
3
, viz.
NO
2
þ O
3
-NO
3
þ O
2
(2.52)
The time constant for reaction (2.52) is of the order of 15 h at an ozone
concentration of 30 ppbv and T ¼ 290 K. Other sources include
N
2
O
5
þ M -NO
3
þ NO
2
þ M (2.53)
but as N
2
O
5
is formed from
NO
3
þ NO
2
þ M -N
2
O
5
þ M (2.54)
the two species act in a coupled manner. Dinitrogen pentoxide, N
2
O
5
, is
potentially an important product as it can react heterogeneously with
water to yield HNO
3
. During the daytime the NO
3
radical is rapidly
photolysed as it strongly absorbs in the visible, viz
NO
3
þ hn -NO þ O
2
(2.55)
40 Chapter 2
NO
3
þ hn -NO
2
þ O(
3
P) (2.56)
having a lifetime in the region of 5 s for overhead sun and clear sky
conditions. Further, NO
3
will react rapidly with NO
NO
3
þ NO -NO
2
þ NO
2
(2.57)
which can have significant daytime concentrations in contrast to the
night time, where away from strong source regions, the NO concentra-
tions should be near zero.
The nitrate radical has a range of reactivity towards VOCs. The
nitrate radical is highly reactive towards certain unsaturated hydrocar-
bons such as isoprene, a variety of butenes and monoterpenes, as well as
reduced sulfur compounds such as dimethylsulfide (DMS). In the case of
DMS, if the NO
2
concentration is 60% that of DMS then NO
3
is a more
important oxidant than OH for DMS in the MBL.
27
In general, NO
3
abstraction reactions of the type
NO
3
þ RH -HNO
3
þ R (2.58)
are relatively slow, with the alkyl radical reacting with oxygen under
atmospheric conditions to form a peroxy radical. In the case of RH being
an aldehyde, acyl products will form acylperoxy radicals (RÁ COÁ O
2
),
potential sources of peroxyacylnitrates. In contrast, the reaction of NO
3
with alkenes occurs by an addition mechanism, initiating a complex
chemistry involving nitrooxy substituted organic radicals, which can
either regenerate NO
2
or produce comparatively stable bifunctional or-
ganic nitrate products.
28
For example, the products derived from the
reaction of NO
3
with propene in the presence of O
2
and NO
x
include
CH
3
CHO, HCHO, 1,2-propanedioldinitrate (PDDN), nitroxyperoxyp-
ropylnitrate (NPPN) and a-(nitrooxy)acetone (See Figure 15).
3
The
reaction channel that produces the nitrated acetones also yields peroxy
radicals, leading to the potential for a night-time source of OH, either by
reaction (HO
2
þ O
3
) or by the direct reaction of the peroxy radical with
NO
3
. For the reaction of NO
3
with propene the initial addition can take
place at either end of the double bond, viz
NO
3
þ CH
2
Q
CHCH
2
þ M -CH
2
CHCH
2
(ONO
2
) þ M (2.59)
NO
3
þ CH
2
Q
CHCH
2
þ M -CH
2
CH(ONO
2
)CH
2
þ M (2.60)
The reaction can then proceed by the mechanism shown schematically in
Figure 15. The ratio of final products is dependent on the structure of
the individual alkenes. In general, for branched alkenes, there is
41 Chemistry of the Atmosphere
significant regeneration of NO
x
and production of unsubstituted car-
bonyl products while comparatively they are a minor source of HO
x
.
28
For the less alkyl substituted alkenes, there is a greater yield of HO
x
and
bifunctional organic nitrate products but a lesser regeneration of NO
x
.
Therefore, depending on the mix of hydrocarbons, NO
3
chemistry can
act to either recycle NO
x
, therefore inhibiting the formation of nitrate
CH
3
CHCH
2
ONO
2
OO
RO
2
NO
3
CH
3
CCHCH
2
ONO
2
O
CH
3
CCH
2
ONO
2
+ HO
2
α-(nitrooxy)acetone
O
O
2
NO
2
PDDN
CH
3
CHO + HCHO
+ NO
2
CH
3
CHCH
2
O
2
ONO
2
RO
2
NO
3
CH
3
CHCH
2
O
ONO
2
NO
2
NPPN
NO
3
O
2
NO
3
O
2
M
M
Figure 15 A schematic representation of the chain propagation reactions in the NO
3
radical initiated oxidation of propene
28
O
3
Aerosol surface
reactions Organic nitrates
N
2
O
5
NO
2
NO
3
NO
2
H
2
O
Aerosol
losses
HNO
3
RH,
DMS
Alkenes
NO, RO
2
Surface losses
O
3
Figure 16 A simplified reaction scheme for night-time chemistry involving the nitrate
radical
27
42 Chapter 2
aerosol or HNO
3
at night and potentially lead to the generation of a
night-time source of HO
x
. Figure 16 provides a simplified summary of
the relevant night-time chemistry involving the nitrate radical.
One important difference between NO
3
chemistry and daytime OH
chemistry is that NO
3
can initiate, but not catalyse, the removal
of organic compounds. Therefore its concentration can be suppressed
by the presence of fast-reacting, with respect to NO
3
, organic com-
pounds.
Reactive lifetime with respect to different oxidants
Different oxidants react at different rates in the atmosphere. Further,
the average concentrations of the main oxidants can vary. For the
following table of data, calculate the relative lifetime with respect to
reaction with OH and NO
3
, given that the average [OH] E 10
6
molecule cm
À3
and the [NO
3
] E 10
9
molecule cm
À3
.
Compound
k(OH) (cm
3
molecule
À1
s
À1
)
t
OH
(days)
k(NO
3
)
(cm
3
mole-
cule
À1
s
À1
t
NO
3
(days)
CH
4
8.5 Â 10
À15
1361 o1 Â 10
À19
115,740
C
2
H
6
2.7 Â 10
À13
43 8 Â 10
À18
1446
C
2
H
4
8.5 Â 10
À12
1.3 2 Â 10
À16
58
(CH
3
)
2
C
Q
C(CH
3
)
2
1.1 Â 10
À10
0.1 4.5 Â 10
À11
2Â10
À4
The data nicely illustrate that lifetime is a product of rate and the
concentration of the radical species.
Case Study III – Evidence for the role of NO
3
in night-time oxidation
chemistry from experimental based studies.
27,28
Significant NO
3
con-
centrations have been detected over a wide range of atmospheric
conditions, indicating a potential role for NO
3
over large regions of
the atmosphere.
28
The atmospheric lifetime of NO
3
can be estimated
using the steady-state approximation (cf. PSS) to be
tðNO
3
Þ ¼
½NO
3
Š
k
52
½NO
2
Š½O
3
Š
ð2:61Þ
43 Chemistry of the Atmosphere
A useful quantity with which to compare this with is the reciprocal of
the lifetime calculated from the sum of the first order loss processes
involving NO
3
and N
2
O
5
tðNO
3
Þ
À1
!
X
i
k
ðNO
3
þHC
i
Þ
½HC
i
Š þk
ðNO
3
þDMSÞ
½DMSŠ þk
het
ðNO
3
Þ
þ k
I
½H
2
OŠ þk
II
½H
2

2
þk
het
ðN
2
O
5
Þ

:K
2:54
½NO
2
Š
ð2:62Þ
where the pseudo first-order loss rates over the i reactive hydrocar-
bons are summed and k
I
and k
II
are the first- and second-order
components with respect to H
2
O of the reaction
N
2
O
5
þ H
2
O -2HNO
3
(2.63)
k
het
(NO
3
) and k
het
(N
2
O
5
) are the heterogeneous loss rates for these
species and K
2.54
is the equilibrium constant for reactions (2.53 and
2.54). Figure 17 shows the observed lifetime of NO
3
in the MBL at
Mace Head, Ireland
29
segregated by arrival wind sector. Mace Head
experiences a range of air masses from clean marine air to European
continental outflow. The measured NO
3
lifetime varies from 2 min to
4 h (see Figure 17). An assessment of the parameters controlling NO
3
atmospheric lifetime (cf. Equation (2.61)) highlights that, under the
conditions encountered the lifetime of NO
3
chemistry is very sensitive
to DMS and NMHC chemistry in clean marine air. However, in
more polluted air the terms involving the indirect loss of N
2
O
5
either
in the gas-phase with H
2
O or through uptake on aerosol tend to
dominate.
From the preceding discussion it can be seen that the involvement of
NO
3
chemistry in gas-phase tropospheric chemistry has potentially six
significant consequences.
28
(i) The radical can control NO
y
speciation in the atmosphere at
night (via reaction (2.54)).
(ii) Nitric acid can be formed, by hydrolysis of N
2
O
5
, as a product of
a hydrogen abstraction process or indirectly via the NO
3
-medi-
ated production of OH, which can react with NO
2
(reaction
(2.23)) to produce nitric acid.
(iii) Primary organic pollutants can be oxidised and removed at night.
(iv) Radicals (HO
x
and RO
2
) produced by NO
3
chemistry can act as
initiators for chain oxidation chemistry.
44 Chapter 2
(v) Toxic or otherwise noxious compounds such as peroxyacylni-
trates, other nitrates and partially oxidised compounds, may be
formed.
(vi) Nitrate products or NO
3
itself may act as temporary reservoirs in
the presence of NO
x
.
[DMS] = 10 pptv
τNO
3
= 57.8 minutes
[DMS] = 44 pptv
τNO
3
= 14.6 minutes
00 10
90
60
30
0
90
60
30
30
30
60 60
00 10
90
60
30
0
90
60
30
30
30
60 60

NO
3
/mins.
Figure 17 Polar plots showing the observed lifetime of NO
3
vs. arrival wind direction for
Mace Head, Ireland (top) and Tenerife (bottom).
29
The black circle repre-
sents the calculated lifetime of NO
3
from reaction with the campaign average
[DMS] only
45 Chemistry of the Atmosphere
2.7 OZONE-ALKENE CHEMISTRY
Another potential dark source of HO
x
in the atmosphere, more partic-
ularly in the boundary layer, is from the reactions between ozone and
alkenes. The ozonolysis of alkenes can lead to the direct production of
the OH radical at varying yields (between 7 and 100%) depending on the
structure of the alkene, normally accompanied by the co-production of
an (organic) peroxy radical. As compared to both the reactions of OH
and NO
3
with alkenes the initial rate of the reaction of ozone with an
alkene is relatively slow, this can be offset under regimes where there are
high concentrations of alkenes and/or ozone. For example, under typical
rural conditions the atmospheric lifetimes for the reaction of ethene with
OH, O
3
and NO
3
are 20 h, 9.7 days and 5.2 months, respectively in
contrast, for the same reactants with 2-methyl-2-butene the atmospheric
lifetimes are 2.0 h, 0.9 h and 0.09 h.
The mechanism for the reaction of ozone with alkenes was first
suggested by Criegee
30
in the late 1940s and involves the addition of
ozone to form a primary ozonide, which rapidly decomposes to form a
vibrationally excited carbonyl oxide (Criegee intermediate) and carbonyl
products. The Criegee intermediate can then either be collisionally
stabilised by a third body (M), or undergo unimolecular decomposition
to products (see also Section 2.8). It is now widely believed that alkyl-
substituted Criegee intermediates can decompose via a vibrationally hot
hydroperoxide intermediate to yield an OH radical, along with another
radical species of the general form R
1
R
2
CC(O)R
3
, which is expected to
react rapidly with O
2
to form a peroxy radical (RO
2
) in the atmos-
phere.
31
Figure 18 shows a schematic representation of the ozone-alkene
reaction mechanism. The OH and peroxy radical yield is dependent on
the structure and mechanism of the individual alkene-ozone reaction.
32
Table 5 shows typical OH yields for the reaction of a range of anthro-
pogenic and biogenic alkenes with ozone. There is growing experimental
evidence
33
of the importance of ozone-alkene reactions as significant
oxidative sinks for alkenes and a general source of HO
x
.
2.8 SULFUR CHEMISTRY
Sulfur chemistry is an integral part of life, owing to its role in plant and
human metabolism. Sulfur compounds have both natural and anthro-
pogenic sources. In modern times, the atmospheric sulfur budget has
become dominated by anthropogenic emissions, particularly from fossil
fuel burning. It is estimated that 75% of the total sulfur emission budget
is dominated by anthropogenic sources with 90% of it occurring in the
46 Chapter 2
R
3
R
1
R
2
R
4
+ O
3
O
O O
R
1
R
2
R
4
R
3
O
O O
R
1
R
2
R
4
R
3
R
1
R
2
O
O
*
+
R
3
R
4
O
α
R
3
R
4
O
O
*
+
R
1
R
2
O (1−α )
R
R'
O
O
*
Stabilisation
R
R'
O
O
*
Decomposition Products
H
O
O
R
H
H
O
O
H
R
H
H
R
O
H
H
+ OH
O O
O
R
O
2
Primary Ozonide
M
Figure 18 A schematic representation of the oxidation of an alkene initiated by reaction
with ozone (after ref. 14)
Table 5 Range of OH yields from the reaction of ozone with alkenes
Alkene OH yield
Ethene 0.18 Æ 0.06
Propene 0.35 Æ 0.07
Methylpropene 0.72 Æ 0.12
D
3
-carene 1.00
Source: All data taken from ref. 32.
47 Chemistry of the Atmosphere
Northern Hemisphere. The natural sources include volcanoes, plants,
soil and biogenic activity in the oceans.
5
In terms of photochemistry the
major sulfur oxide, sulfur dioxide (SO
2
) does not photodissociate in the
troposphere (cf. NO
2
), i.e.
SO
2
(X
1
A
1
) þ hn(240 olo 330 nm) -SO
2
(
1
A
2
,
1
B
1
) (2.64)
SO
2
(X
1
A
1
) þ hn(340 olo 400 nm) -SO
2
(
3
B
1
) (2.65)
The oxidation of sulfur compounds in the atmosphere has implications
in a number of different atmospheric problems such as acidification,
climate balance and the formation of a sulfate layer in the stratosphere,
the so-called Junge layer. By far the largest sulfur component emitted
into the atmosphere is SO
2
. Figure 19 shows the spatial distribution of
SO
2
emissions in 1980 and 2000 from EMEP.
34
In Europe, the source
regions for SO
2
are quite apparent, the so-called black triangle region
(southern Poland, eastern Germany and the northern part of the Czech
Republic) are the largest sources of anthropogenic sulfur pollution.
There are a number of other large emission sources including central
UK and the Kola Peninsula, also apparent in Figure 19. The absolute
maximum in emissions is in southern Italy around Sicily where the
largest single source of both natural, the volcano Mt. Etna, and anthro-
pogenic SO
2
is found. SO
2
can be detected from space-borne sensors
35
as
a product of volcanic activity and fossil fuel burning. Figure 19 also
illustrates another interesting point in that over much of Europe between
1980 and 2000 there has been a decrease of 1000 ton or more owing
to legislative limits. Interestingly, with decreasing land emissions the
importance of ship emissions has increased (from 5% to 16% of total
European SO
2
emissions).
The atmospheric oxidation of SO
2
can take place by a number of
different mechanisms, both homogeneously and heterogeneously in the
liquid and gas phases (see Figure 20). The gas-phase oxidation of SO
2
, viz
SO
2
þ OH þ M -HSO
3
þ M (2.66)
HSO
3
þ O
2
-HO
2
þ SO
3
(2.67)
SO
2
þ H
2
O þ M -H
2
SO
4
(2.68)
can lead to the formation of sulfuric acid, which owing to its relatively
low vapour pressure can rapidly attach to the condensed phase such as
48 Chapter 2
aerosol particles. The bulk of the H
2
SO
4
is lost via wet deposition
mechanisms in cloud droplets and precipitation. There is another po-
tential gas-phase loss route for SO
2
that can lead to the formation of
sulfuric acid in the presence of H
2
O, i.e. the reaction of SO
2
with Criegee
intermediates (see Section 2.7). The aqueous-phase oxidation of SO
2
is
(a)
(b)
SO
2
Mg
50000
10000
5000
1000
500
100
50000
10000
5000
1000
500
100
Mg
100
80
60
40
20
0
0 30 60 90 120
100
80
60
40
20
20 40 60 80 100 120
Figure 19 Spatial distributions of sulfur dioxide emissions in (a) 1980 and (b) 2000.
34
The units are ton year
À1
grid sq
À1
49 Chemistry of the Atmosphere
more complex, depending on a number of factors such as the nature of
the aqueous phase (e.g. clouds and fogs), the availability of oxidants
(e.g. O
3
and H
2
O
2
) and the availability of light. An overview of the
mechanism is given in Figure 20. The key steps include the transport of
the gas to the surface of a droplet, transfer across the gas–liquid
interface, the formation of aqueous-phase equilibria, the transport
from the surface into the bulk aqueous phase and subsequent reac-
tion. In brief, the SO
2
gas is dissolved in the liquid phase, establishing
a set of equilibria for a series of S(IV) species, i.e. SO
2
H
2
O, HSO
3
À
and SO
3

.
SO
2
(g) þ H
2
O "SO
2
d
H
2
O(aq) (2.69)
SO
2
d
H
2
O(aq) "HSO
À
3
þ H
1
(2.70)
HSO
À
3
"SO

3
þ H
1
(2.71)
The solubility of SO
2
is related to the pH of the aqueous phase,
decreasing at lower values of pH. The oxidation of sulfur (IV) to sulfur
(VI) is a complex process dependent on many physical and chemical
factors. The main oxidants seem to be O
2
(catalysed/uncatalysed), O
3
,
H
2
O
2
, the oxides of nitrogen and free-radical reactions in clouds and
fogs. For example, H
2
O
2
is highly soluble in solution so even at rela-
tively low gas-phase concentrations (typically ca. 1 ppbv) there is a
Figure 20 Summary of emission, oxidation and deposition of S(IV) and S(VI) (after
ref. 63)
50 Chapter 2
significant concentration of H
2
O
2
present in solution. The oxidation
proceeds as
HSO
3

+ H
2
O
2
O
O

OOH S H +
2
O
ð2:72Þ
O
O

OOH S + HA H
2
SO
4
+ A

ð2:73Þ
where HA is an acid. The ubiquitous occurrence of H
2
O
2
, its solubility,
its high reactivity and pH independence (under atmospheric conditions)
of the rate constant for the reaction with SO
2
makes H
2
O
2
one of the
most important oxidants for SO
2
in the troposphere. A more detailed
description of aqueous-phase oxidation of SO
2
is given in ref. 36.
2.9 HALOGEN CHEMISTRY
In comparison to the atmospheric chemistry taking place in the strat-
osphere where halogen chemistry is well known and characterised (see
Section 2.10), there has been much debate as to the role of halogen
species in the oxidative chemistry of the troposphere. There is growing
experimental evidence as to the prevalence of halogen chemistry as part
of tropospheric photochemistry (see Table 6).
14,37
Much of the proposed
halogen chemistry is propagated through the reactions of a series of
halogen atoms and radicals.
Table 6 Sources of reactive halogen species found in various parts of the
troposphere
Species, site Likely source mechanism
ClO
x
in the polar
boundary layer
By-product of the ‘‘Bromine Explosion’’
ClO
x
by salt flats By-product of the ‘‘Bromine Explosion’’
BrO
x
in the polar
boundary layer
Autocatalytic release from sea-salt on ice, ‘‘Bromine explosion’’
mechanism
BrO
x
in the Dead sea
basin
‘‘Bromine Explosion’’ (salt pans)
BrO
x
in the free
troposphere
(1) Photo-degradation of hydrogen-containing organo-halogen
species (e.g. CH
3
Br), (2) ‘‘Spill-out’’ from the boundary
layer, (3) Transport from the stratosphere?
BrO
x
in the MBL ‘‘Bromine Explosion’’ mechanism
IO
x
in the MBL (1) Photo-degradation of short-lived organo-halogen species
(e.g. CH
2
I
2
) (2) Photolysis of I
2
?
Source: After ref. 37.
51 Chemistry of the Atmosphere
Bromine oxide species can be formed in the polar boundary layer
38,39
and areas with high salt levels such as the Dead Sea.
40
The major source
of gas-phase bromine in the lower troposphere is thought to be the
release of species such as IBr, ICl, Br
2
and BrCl from sea-salt aerosol,
following the uptake from the gas phase and subsequent reactions of
hypohalous acids (HOX, where X ¼ Br, Cl, I).
41
HOBr þ (Br
À
)
aq
þ H
1
-Br
2
þ H
2
O (2.74)
The halogen release mechanism is autocatalytic
38
and has become
known as the ‘‘Bromine explosion’’. The Br
2
produced in reaction
(2.74) is rapidly photolysed, producing bromine atoms that can be
oxidised to BrO by O
3
(reaction (2.76))
BrX þ hn -Br þ X (2.75)
Br þ O
3
-BrO þ O
2
(2.76)
the resultant BrO reacting with HO
2
(reaction (2.77)) to reform HOBr.
BrO þ HO
2
-HOBr þ O
2
(2.77)
Thus, the complete cycle has the form
BrOþO
3
þðBr
À
Þ
aq
þðH
þ
Þ
aq
À!
surface; HO
x
2BrOþproducts ð2:78Þ
where effectively one BrO molecule is converted to two by oxidation of
bromide from a suitable surface. Figure 21 shows a schematic represen-
tation of the Bromine-explosion mechanism.
37
It is worth noting that the
bromine explosion mechanism only occurs from sea salt with a pHo6.5
therefore requiring acidification of the aerosol potentially caused by the
uptake of strong acids likely to be of anthropogenic origins or naturally
occurring acids.
42,43
The wide-spread occurrence of these heterogeneous
mechanisms are supported by the observed depletion of bromide ions in
sea-salt aerosol.
42,43
Case Study IV – BrO in the springtime Arctic – In the spring time in
both the Arctic and Antarctic large clouds of BrO-enriched air masses
are observable from space (see Figure 22).
44,45
These clouds cover
several thousand square kilometres over the polar sea ice with BrO
levels up to 30 pptv. The BrO is always coincident with low levels of
ozone in the MBL.
38
In order to observe these events, there is a
requirement for meteorological conditions that stop mixing between
52 Chapter 2
the boundary layer and the free troposphere and sunlight to drive the
required photolysis of gaseous bromine (see reaction (2.75)) released
heterogeneously through chemical processes on the ice. Because of the
prerequisites for strong surface inversions to confine the air and
sunlight, episodes of bromine explosion events and boundary layer
ozone depletion tend to be confined to spring. It is thought that frost
flowers in the Antarctic, which are formed on a liquid layer with high
salinity on top of the sea ice surface, are likely to provide a large
surface area for the heterogeneous release of reactive bromine but the
evidence is not unequivocal.
With respect to iodine chemistry, the major sources of iodine are
thought to be from macroalgal sources releasing organoiodine com-
pounds.
46
Photolysis of the organoiodine compounds releases the iodine.
RI
x
þ hn -R þ I (2.79)
I þ O
3
-IO þ O
2
(2.80)
During daylight hours iodine monoxide, IO exists in a fast photochem-
ical equilibrium with I, viz.
IO þ hn -I þ O (2.81)
Heterogeneous release of bromine
on sea salt surfaces
O H g Br H aq Br g HOBr
O HOBr HO BrO
2 2
2 2
) ( ) ( ) ( + → + +
+ → +
+ −
Catalytical ozone destruction
2
,
3
3 2 O O
BrO Br
→
The Bromine explosion
HOBr
HOBr
HOBr
Br
2
+Br
-
+BrO
BrO
Br
h
ν
+HO
2
+O
3
Sea ice surface
Aerosol
Figure 21 A schematic representation of the so-called Bromine explosion mechanism
where effectively one BrO molecule is converted to two by oxidation of
bromide from a suitable aerosol surface
64
53 Chemistry of the Atmosphere
The aerosol ‘‘explosion’’ mechanism, previously described for bromine,
acts effectively to recycle the iodine back to the gas phase.
Case Study V – Iodine monoxide chemistry in the coastal margins –
Figure 23 shows the measured concentration of iodine monoxide (IO)
>8
7
6
5
4
3
2
>1
BrO VC
[x10
13
molec/cm
2
]
GOME BrO, Mar 2000
Gwin DOAS 1.02, Oct.2000
IASB-BIRA
DLR
ESA-ESRIN
BIRA-IASB
Contact : michelv@oma.be
GOME BrO, Oct 1999
>8
7
6
5
4
3
2
>1
BrO VC
[x10
13
molec/cm
2
]
Figure 22 [BrO] in the Antarctic and Artic during spring derived from GOME satellite
measurements
45
54 Chapter 2
at Mace Head in Ireland.
47
The data in Figure 23 show not only a
clear requirement for radiation for photochemical production of IO
but also a strong correlation with low tide conditions. The correlation
with low tidal conditions is indicative of the likely sources of IO, in
that the photolysis of organoiodine compounds (reaction (2.79)) such
as CH
2
I
2
and CH
2
IBr emitted from macroalgae in the intertidal zone
are possibly the candidate iodine sources. The photolysis lifetime of a
molecule such as diodomethane is only a few minutes at midday.
Recent experimental observations have suggested the I
2
can be emit-
ted directly from the macroalgae at low tide making this a substantial
source of iodine.
48
The chemistry can also lead to an enrichment of
iodine in the aerosol in the form of iodate providing a route to move
biogenic iodine from ocean to land.
47
Figure 23 [IO], tidal height and solar radiation measured at Mace Head in Ireland. The
grey areas represent the low-tide areas during the day. The dotted line in the
upper panel is the IO detection limit
46,47
55 Chemistry of the Atmosphere
2.9.1 Tropospheric Halogens and Catalytic Destruction of Ozone
Potentially, the most important effect of reactive halogen species maybe
that their chemistry may lead to the catalytic destruction of ozone via
two distinct cycles
Cycle I:
XO þ YO -X þ Y þ O
2
(or XY þ O
2
) (2.82)
X þ O
3
-XO þ O
2
(2.83)
Net:
O
3
þ O
3
-3O
2
(2.84)
In Cycle I, the rate-limiting step involves reaction (2.82), the self- or
cross-reaction of the halogen monoxide radicals. Cycle I has been
identified to be the prime cause for polar boundary layer ozone destruc-
tion.
38
The second-ozone destruction cycle, which is more prevalent at
low halogen levels, has the form
Cycle II:
XO þ HO
2
-HOX þ O
2
(2.85)
HOX þ hn -X þ OH (2.86)
X þ O
3
-XO þ O
2
(2.83)
OH þ CO -H þ CO
2
(þM) -HO
2
(2.11, 2.12)
Net: O
3
þ CO þ hn -CO
2
þ O
2
(2.87)
The rate-determining step in this reaction sequence is reaction (reaction
(2.85)) making ozone destruction linearly dependent on [XO]. The
fraction of HOX that photolyses to give back OH depends critically
on the accommodation coefficient of HOX on aerosols. Currently, there
is a large uncertainty in this parameter. An important side effect of Cycle
II is the potential for the reduction of the [HO
2
]/[OH] ratio by con-
sumption of HO
2
. The inorganic halogen chemistry described is sum-
marised in Figure 24.
56 Chapter 2
Case Study VI – The potential effect of tropospheric halogen chemistry
on ozone – An example of the potential effect of the ozone depletion
cycles (Cycles I and II) can be assessed using data from the MBL.
49
Table 7 lists the rates of ozone depletion (from Cycles I and II) in the
first hour after sunrise at Mace Head in Ireland. Measurements of
Figure 24 Simplified scheme of the inorganic halogen reactions in the boundary layer (X
¼ Cl, Br, I). The reactive halogen sources are release from sea salt or
photochemical degradation of organohalogen species
37
Table 7 Rates of ozone depletion by various catalytic cycles involving XO using
measured data typical of MBL just after sunrise
Rate-determining reaction Cycle (see text) O
3
removal rate (ppbv h
À1
)
BrO þ IO I 0.13
IO þ HO2 II 0.08
IO þ IO I 0.06
BrO þ HO2 II 0.03
BrO þ BrO I 0.01
Source: After ref. 48.
Note: All rates calculated at T ¼ 295 K for BrO ¼ 3 pptv, IO ¼ 2 pptv and HO
2
¼ 3 pptv.
57 Chemistry of the Atmosphere
[BrO] show a pulse in the first two hours after dawn ascribed to the
photolysis of inorganic bromine compounds produced either by the
bromine explosion mechanism
41
or the photolysis of mixed bromo/
iodo-organohalogens
46
built up overnight. Using measured concen-
trations of BrO, IO and HO
2
, the data in Table 7 show the ozone
depletion cycle (Cycle type I) involving the BrO and IO cross-reaction
is the most important with an O
3
depletion rate of 0.3 ppbv h
À1
.
2.10 STRATOSPHERIC CHEMISTRY
The stratosphere is characterised by increasing temperatures with in-
creasing height (see Figure 1). The presence of ozone and oxygen that
absorb the UV light and emit infrared radiation heats this region.
Approximately, 90% of ozone molecules are found in the stratosphere
(see Figure 6). The chemistry of the stratosphere, as compared to that of
the troposphere, maybe described as being more chemically simple but
initiated by shorter wavelength (more energetic) light.
A British scientist Sydney Chapman
50
suggested the basic ideas of
stratospheric ozone in the 1930s, which have become known as the
Chapman cycle. Short wavelength UV (hn) can dissociate molecular
oxygen and the atomic oxygen fragments produced react with oxygen
molecules to make ozone.
O
2
þ hn -O þ O (2.88)
OþO
2
À!
M
O
3
ð2:20Þ
There are some further reactions that complete the picture, which are
involved in the interconversion and removal of ozone and atomic
oxygen
O
3
þ hn -O þ O
2
(2.89)
O þ O
3
-O
2
þ O
2
(2.90)
As O and O
3
can rapidly interconvert (reactions (2.89 and 2.90)) they are
often referred to as odd oxygen.
Even from this simple chemistry, it is possible to see why there is an
ozone layer (see Figure 6). For the production of ozone, both UV
radiation (hn) and molecular oxygen are required (O
2
). High up in the
atmosphere there is a plentiful supply of short-wavelength UV radiation
but little oxygen, lower down in the atmosphere the opposite situation
58 Chapter 2
pertains. Thus, the point where there is both enough molecular oxygen
and UV light is where the maximum in the ozone concentrations are
going to be found. In the terrestrial atmosphere this point is at a height
of about 15–40 km, as shown in Figure 6. When the Chapman oxygen-
only mechanism is applied to real atmospheric measurements, it is
found that about five times as much ozone is predicted as is measured.
This therefore follows that there must be some other, faster, way of
removing ozone in the stratosphere. One idea put forward by Bates and
Nicolet
51
is that a catalytic process could be speeding up the destruction
of ozone. A catalyst is something that can promote a chemical reaction
without itself being consumed. In the stratosphere, a catalytic cycle
like
X þ O
3
-XO þ O
2
(2.83)
O þ XO -X þ O
2
(2.91)
Net O þ O
3
-O
2
þ O
2
(2.90)
can lead to the net destruction of ozone (reaction (2.90)). In this case the
catalyst is the molecule X, which by destroying ozone is converted into
XO, but the XO then reacts with an oxygen reforming X. This, the so-
called chain process, can proceed many hundreds of thousands of times
before termination. As to the identity of X, it is molecules like chlorine
atoms (Cl), nitrogen oxide (NO) and the hydroxyl radical (OH) and
therefore the corresponding XO is ClO, NO
2
and HO
2
, i.e.
Cl þ O
3
-ClO þ O
2
(2.92)
O þ ClO -Cl þ O
2
(2.93)
These cycles are often referred to as the HO
x
, NO
x
and ClO
x
cycles and
the groups of species as families.
On the surface there is now an apparent contradiction; with only the
Chapman cycle we produce too much ozone, whereas the catalytic cycles
could destroy all the ozone! There are a number of cycles that can
interconvert the catalytic cycles without odd oxygen removal these will
be in competition with the catalytic cycles, e.g.
NO þ O
3
-NO
2
þ O
2
(2.24)
59 Chemistry of the Atmosphere
NO
2
þ hn -NO þ O (2.2)
Net O
3
þ hn -O
2
þ O (2.89)
The products of reaction (2.2) recombining via reaction (2.20) to reform
ozone. This form of cycle (2.24, 2.2, 2.89) is often referred to as a null
cycle. The fraction of the XO
x
tied up in null cycles is ineffective as a
catalyst.
Another key feature with respect to the effectiveness of catalytic cycles
is the formation of reservoir species via holding cycles. At any given time
about 99% of active Cl is held as reservoir species.
Cl þ CH
4
-HCl þ CH
3
(2.94)
Cl þ H
2
-HCl þ H (2.95)
ClOþNO
2
À!
M
ClONO
2
ð2:96Þ
These reservoirs are of great importance to the chemistry of the strat-
osphere as they act to divert potential catalytic species from active to
inactive forms, but they remain available to release the active catalysts
again. HCl is the longest-lived and most abundant Cl reservoir species
having a lifetime of about one month in the lower stratosphere. It is
returned to active Cl largely via reaction with OH
OH þ HCl -Cl þ H
2
O (2.97)
ClONO
2
formed via reaction (2.96) is destroyed mainly by photolysis or
via reaction with O atoms, leading to regeneration of active Cl species.
ClONO
2
þ hn -Cl þ NO
3
(2.98a)
ClONO
2
þ hn -ClO þ NO
2
(2.98b)
O þ ClONO
2
-Products (2.99)
The lifetime of ClONO
2
is approximately 6 h in the lower stratosphere
(o30 km) decreasing to about an hour at 40 km owing to the increase in
UV light. Figure 25 shows the key chemical interconversions of the
chlorine chemistry in the stratosphere, delineating the molecules into
source, active and reservoir species.
Where do these catalytic species come from and what effect does man
have in increasing the levels of these catalysts? The catalytic families of
60 Chapter 2
HO
x
, NO
x
and ClO
x
are present in the natural atmosphere but in the
contemporary atmosphere these have been supplemented by anthro-
pogenic sources. For example, with the chlorine species the most
abundant natural precursor is methyl chloride, CH
3
Cl. There is little
interhemispheric difference in the concentration of CH
3
Cl indicative of
a strong oceanic source, though there is a rising contribution for
biomass burning as well as small contribution from volcanic emission.
52
As CH
3
Cl has a tropospheric lifetime of a year, it can be transported to
the stratosphere where on reaction with OH or via photolysis it can
release the chlorine. Figure 26 shows the primary sources of chlorine
species for the stratosphere separating the anthropogenic and biogenic
source categories.
There are a number of potential sources of anthropogenic pollution
that could find there way to the stratosphere. One of the first problems
that scientists were worried about was Concorde or stratospheric su-
personic transport (SST). Aircraft engines produce large amounts of
nitrogen oxides (e.g. NO) on combustion of the fuel. Injection of these
nitrogen oxides directly into the atmosphere could supplement the
relevant catalytic cycle plus they can be very long-lived at high altitudes.
Initial estimates suggested that SST would lead to substantial losses of
Chlorine Chemistry in Stratosphere
CH
3
Cl
CFCl
3
ClONO
2
HCl
HOCl
ClO Cl
NO
2
HO
2
NO
OH
OH


O
3
O(
3
P)
Loss cycles

NULL CYCLE
ACTIVE SPECIES
RESERVOIRS
SOURCE GASES O
3
Figure 25 Inorganic chemistry involved in the interconversion chlorine species in the
stratosphere. The relationship between source gases, active species and reser-
voir species is illustrated
61 Chemistry of the Atmosphere
ozone. For two reasons it became apparent that this would not be the
case. First, the number of aeroplanes required to observe a loss of ozone
would be 1500, flying 7 h a day, 7 days a week. This number of
aeroplanes would be able to transport the population of London to
New York, or vice versa in a matter of weeks. Second, refinements to the
understanding of the fundamental chemistry used to make the initial
predictions have shown the impact is likely to be less. A warning note
should be interposed at this point because the rise in international air
travel and the new generation of aircraft means that this problem is back
on the scientific agenda.
53,54
The potential of subsonic aircraft to pollute
the upper atmosphere is now being studied extensively. Other areas of
potential stratospheric pollution have been identified such as NASA
space shuttle launches and the extensive use of agricultural fertilisers.
H
u
m
a
n
-
m
a
d
e

s
o
u
r
c
e
s
Natural
Sources
3000
2000
1000
0
1%
4%
5%
7%
12%
23%
32%
16%
Primary Sources of Chlorine and Bromine for
the Stratosphere in 1999
Chlorine source gases
Other gases
Methyl chloroform (CH
3
OCl
3
)
HCFC
3
(e.g. HCFC22-CHCIF
2
)
CFC-113 (CCl
2
FCCF
2
)
Carbon tetrachloride (CCl
4
)
CFC-11 (CCl
3
-F)
CFC-12 (CCl
2
F
2
)
Methyl chloride (CH
3
Cl)
T
o
t
a
l

c
h
l
o
r
i
n
e

a
m
o
u
n
t

(
p
a
r
t
s

p
e
r

t
r
i
l
l
i
o
n
)
Figure 26 Stratospheric source gases – A variety of gases transport chlorine into the
stratosphere. These gases are emitted from natural sources and human activ-
ities. For chlorine, human activities account for most that reaches the strat-
osphere. The CFCs are the most abundant of the chlorine-containing gases
released in human activities. Methyl chloride is the most important natural
source of chlorine
58
62 Chapter 2
A more serious culprit with respect to the depletion of the atmospheric
ozone layer was identified from about 1974 onwards. US scientists
postulated
55
that some industrial chemical starting to reach the strato-
sphere might interfere with the mechanisms of ozone formation and
destruction. The chemicals were chlorofluorocarbons, or CFCs, and had
been introduced by General Motors in the 1930s mainly as coolants for
refrigerators and air conditioning systems, aerosol propellants and
blowing agents, etc. The perceived virtue of these compounds was their
physical properties, chemical inertness and lack of toxicity. The poten-
tial problem becomes apparent at higher altitudes where the CFCs (e.g.
CF
2
Cl
2
) are not so inert and can be broken down by UV light
CF
2
Cl
2
þ hn -Cl þ CF
2
Cl (2.100)
releasing a chlorine atom that can enter the previously described cata-
lytic cycles (reactions (2.92 and 2.93)) and destroy ozone. Fortuitously,
as described previously, most of the active chlorine, including that
provided by CFC degradation is tied up in the reservoir compounds.
There are many myths about CFCs and chlorine in the atmosphere, such
as if CFCs are heavier than air how can they make it high up into the
atmosphere? The truth is that thousands of measurements have found
CFCs high in the atmosphere and though heavier than air, the atmos-
phere is not still and the winds can carry and mix gases high into the
stratosphere.
52
Figure 26 shows the amount and variety of CFC com-
pounds that can act as source gases for chlorine in the stratosphere.
Based on predictions of the effect of CFCs on the ozone layer, in 1987
a previously unprecedented step was taken when many countries signed
the UN Montreal protocol specifying the control and phase-out of these
ozone-depleting chemicals.
52
Since that time the protocol has been
modified in order to speed up the schedule and extend the range of
chemical covered to further lessen the effect of these chemicals (see
Figure 27). One of the factors that lead to more rapid world action on
CFCs was the discovery of the so-called Antarctic ozone hole.
2.10.1 The Antarctic Ozone Hole
British scientists from the British Antarctic Survey (BAS) had been
making measurements of ozone from their base at Halley Bay (761S) for
many years. They detected a decline in the springtime ozone since 1977,
and by October 1984, they had detected a 30% decline in the total
ozone.
56
Today, this value has reached 60%. The ozone hole begins to
develop in August, is fully developed by early October and has normally
broken up by early December (see Figure 28).
63 Chemistry of the Atmosphere
Figure 29 shows a recent picture of the ozone hole taken from space.
Strictly speaking the use of the word ‘‘hole’’ to describe what happens to
ozone in the Antarctic is an exaggeration. There is undoubtedly a
massive depletion of ozone, particularly between 12 and 20 km in the
Antarctic stratosphere (up to 100%) but the total column of ozone is
depleted rather than removed altogether (see Figure 28). The exact
location and size of the hole varies with meteorological conditions, but
the area covered has increased over the past 10 years or so (see Figure
30). Currently, in the austral spring the hole extends over the entire
Antarctic continent, occasionally including the tip of South America,
covering an area equivalent to the North American continent (ca. 22
million km
2
) (see Figure 31).
Effect of the Montreal Protocol
20000
15000
10000
5000
0
1980 2000 2020 2040 2060 2080 2100
Year
P
r
e
d
i
c
t
e
d

a
b
u
n
d
a
n
c
e

(
p
a
r
t
s

p
e
r

m
i
l
l
i
o
n
)
Effective stratospheric
chlorine
No protocol
London 1990
Copenhagen
1992
Montreal
1987
Zero emissions
Beijing
1999
Figure 27 Predictions for the future abundance of effective stratospheric chlorine are
shown in (1) the assuming no Protocol regulations, (2) only the regulations in
the original 1987 Montreal Protocol and (3) additional regulations from the
subsequent Amendments and Adjustments. The city names and years indicate
where and when changes to the original 1987 Protocol provisions were agreed
upon. Effective stratospheric chlorine as used here accounts for the combined
effect of chlorine and bromine gases. The ‘‘zero emissions’’ line shows strato-
spheric abundances if all emissions were reduced to zero beginning in 2003
58
64 Chapter 2
0 5 10 15 0 5 10 15
Ozone abundance (mPa)
30
25
20
15
10
5
0
Polar Ozone Depletion
Antarctic Ozone
South Pole (90°S)
A
l
t
i
t
u
d
e

(
k
m
)
A
l
t
i
t
u
d
e

(
m
i
l
e
s
)
15
10
5
0
Arctic Ozone
Sodankyla,
Finland (67°N)
Figure 28 Antarctic and Artic ozone distributions in the SH and NH spring periods.
58
The figure shows the substantial decrease in ozone in the 14–20 km range after
polar sunrise. For the Antarctic the data show there was little depletion before
the 1980s. For the Arctic, there is substantial interannual variability owing to
the temperature of the stratosphere
Earth Probe TOMS Total Ozone, September 16, 2000
<120 200 280 360 440 520>
Ozone (Dobson Units)
Figure 29 The 2000 ozone hole over the Antarctic seen by the satellite EP-TOMS (Image
courtesy of NASA)
65 Chemistry of the Atmosphere
What happens in Antarctic stratosphere to make it different from
many other places? It is colder than the rest of the earth, ozone depletion
occurs in the Austral spring when it is particularly cold (À801C). Polar
meteorology leads to very strong westerly winds (up to 100 ms
À1
)
forming a stable vortex, which prevents mixing of air from lower
latitudes (see Figure 32). The vortex develops a core of very cold air
and it is these temperatures that allow polar stratospheric clouds (PSCs)
to form. When the sun returns in September, the temperatures begin to
rise, the winds weaken and typically this drives the vortex to break down
by November. In a sense the air over the pole is more or less confined
into what can be thought of as a giant chemical reactor. There is a slow
downward circulation (see Figure 32), which draws air down through
the vortex modifying this to a notional flow reactor.
In 1986 and 1987, a huge international expedition was mounted to
examine the chemistry and meteorology that leads to the polar ozone
loss. Many different measurements were made using satellites, aero-
planes and ground-based instruments.
57
The results showed some stark
200
180
160
140
M
n
i
m
u
m

o
z
o
n
e

(
D
U
)
120
100
80
1980 1985 1990
Year
1995 2000 2005
209
205 205
9/17
10/1510/10
189
9/25
10/18
169
154
159
173
146
9/19
Antarctic ozone minimum (60° - 90° S)
120
124
128
117
124
94
88
111
104
90
92
94
99
97
140
9/9
9/28
9/26
9/29
9/5
9/30
9/24
10/5
9/28
10/6
10/10
10/5
10/7
10/4
10/5
10/24
10/7
10/3
1979 - 1992 Nimbus 7 TOMS
1993 - 1994 Meteor 3 TOMS
1995 (no TOMS in orbit)
1996 - 2003 Earth Probe TOMS
Figure 30 Lowest values of ozone measured from satellite each year in the ozone hole.
Global average ozone is about 300 Dobson Units. Before 1980 ozone less than
200 Dobson Units was rarely seen. In recent years ozone near 100 Dobson
Units has become normal in the ozone hole. Ozone in the year 2002 ozone hole
was higher than we have come to expect because of unusually high tempera-
tures in the Antarctic stratosphere (from NASA data)
66 Chapter 2
contrasts between the chemistry inside and outside the vortex before and
after sunrise in the Austral spring (see Figure 33). Within the vortex
concentrations of e.g. ClO were a factor of 10 larger than outside. These
measurements also showed that the stratosphere within the disturbed
region was abnormally dry and highly deficient in nitrogen oxides.
The reason for the dehydration and denitrification of the Antarctic
stratosphere is the formation of the PSCs, whose chemistry perturbs the
composition in the Antarctic stratosphere. Polar stratospheric clouds
can be composed of small (o1 mm diameter) particles rich in HNO
3
or
at lower temperatures (o190 K) larger (10 mm) mainly ice particles.
These are often split into two categories, the so-called Type I PSC, which
contains the nitric acid either in the form of liquid ternary solutions with
water and sulfuric acid or as solid hydrates of nitric acid, or Type II
PSCs made of ice particles. The ice crystals on these clouds provide a
surface for reactions such as
ClONO
2
(g) þ HCl (ice) -Cl
2
(g) þ HNO
3
(ice) (2.101)
Average area of Ozone Hole
area of North America
area of North Antarctica
area of ozone <220 DU
average over 30 days
vertical line = minimum and maximum area
S
i
z
e

(
m
i
l
l
i
o
n

s
q

k
m
)
Year
Figure 31 Growth of the average area of the ozone hole from 1979 to 2003. The ozone
hole is defined as the area for which ozone is less than 220 Dobson Units, a
value rarely seen under normal conditions. It shows that the ozone in this area
hardly occurred at all in 1980, but by year 2000 covered an area larger than
North America, 26.5 million km
2
(from NASA data)
67 Chemistry of the Atmosphere
ClONO
2
(g) þ H
2
O (ice) -HOCl (g) þ HNO
3
(ice) (2.102)
HOCl (g) þ HCl (ice) -Cl
2
(g) þ H
2
O (ice) (2.103)
N
2
O
5
(g) þ H
2
O (ice) -2HNO
3
(ice) (2.104)
In reactions (2.101 and 2.102), the normally inactive reservoir for Cl and
ClO is converted into molecular chlorine. It is worth noting that the
HNO
3
is left in the ice-phase. These reactions can continue all winter
long without light converting inactive chlorine to active chlorine. The
two main effects therefore of the heterogeneous chemistry involving
Figure 32 The Winter vortex over Antarctica. The cold core is almost isolates from the
rest of the atmosphere, and acts as a reaction vessel in which chlorine activation
may take place in the polar night (after ref. 3)
68 Chapter 2
PSCs are the release of active chlorine from its usual reservoirs and the
removal of NO
x
from the system by the production of HNO
3
.
When the sun rises in the spring it triggers the depletion chemistry.
Cl
2
þ hn -Cl þ Cl (2.105)
Cl þ O
3
-ClO þ O
2
(2.92)
But there is one further unforeseen modification as the concentration of
oxygen atoms is too low first thing in spring to regenerate Cl via the
normal reaction (2.93), so there is instead a further low-temperature
reaction that regenerates the chlorine atoms
ClO þ ClO þ M -(ClO)
2
þ M (2.106)
(ClO)
2
þ hn -Cl þ ClOO (2.107)
ClOO þ M -Cl þ O
2
þ M (2.108)
that can re-enter the catalytic cycle and destroy large amounts of ozone.
The absence of significant concentrations of NO
x
stops rapid
CFC11
ClO
BrO
H
2
O
NO
y
N
2
O
~0.75 ppbv
~5 pptv
3.5 ppmv
250 ppbv
10 ppbv
60°S 65°S 70°S
Polewards
Chemically perturbed
region
Observations of stratospheric constituents from ER2 aircraft
Figure 33 Schematic representations of the changes in the concentration of some strato-
spheric species on entering the chemically perturbed region of the Antarctic
vortex (after ref. 57)
69 Chemistry of the Atmosphere
reformation of the ClO
x
reservoir species (e.g. via reaction (2.96)). The
ClO self-reaction ozone destruction cycle is supplemented by a coupled
ClO/BrO cycle.
ClO þ BrO -Cl þ Br þ O
2
(2.109)
or
ClOþBrO !BrCl þO
2
BrCl þhv !Cl þBr
&
ð2:110; 2:111Þ
Cl þ O
3
-ClO þ O
2
(2.92)
Br þ O
3
-BrO þ O
2
(2.76)
The stratospheric bromine comes from a range of source gases including
CH
3
Br.
58
The contribution of bromine to ozone loss in the polar regions
has increased faster than that of chlorine because abundances of bro-
mine continue to increase at a time when those of chlorine are levelling
off (see Figure 27).
52
Cycles (2.105, 2.92, 2.106–2.108) and (2.76, 2.92,
2.109–2.111) account for most of the ozone loss observed in the Ant-
arctic stratosphere in the late winter/spring season. At high ClO abun-
dances, the rate of ozone destruction can reach 2–3% day
À1
in late
winter/spring.
Figure 34 shows a summary of the photochemistry and dynamics in
the polar stratosphere, illustrating the time profiles of the key chlorine
species coupled to the temperature requirements in the vortex. Figure 35
shows measurements of a range of chemical species and temperature in
the 2004 ozone hole. The data reflects the main chemical and physical
features on the ozone hole.
In summary, the key features of Antarctic ozone loss are
(i) The circulating winds in the polar regions enable the formation of
a stable vortex which provides a gigantic ‘‘reaction vessel’’ for
ozone depletion to occur within.
(ii) The low temperatures in the vortex encourage the formation of
PSCs, which enhance the production of active chlorine species.
(iii) Pre-conditioning of the atmosphere takes place during the polar
winter releasing chlorine from reservoir molecules.
(iv) At sunrise, molecular chlorine is dissociated into free atoms that
can destroy the ozone.
(v) Chlorine atoms are regenerated by the dimer reactions.
70 Chapter 2
Inactive
chlorine
Active
chlorine
Inactive
chlorine
Gas-phase
reactions
Surface
reactions
ClONO
2
HCl
(Cl
2
+ClO+(ClO)
2
)
Autumn Early Winter Late Spring Time
ClONO
2
HCl
Denitrification and dehydration
A
b
u
n
d
a
n
c
e
Surface processing
Cl-catalysed O
3
destruction
Inactive chlorine recovery
Breakup
Polar vortex
evolution
Formation,
Cooling,
descent
Maximum intensity
T
e
m
p
e
r
a
t
u
r
e
Time
Figure 34 Photochemistry and dynamics in the polar stratosphere (after ref. 65)
Figure 35 Chemical species and temperature as measured by satellite in the 2004 ozone
hole (image courtesy of NASA). The white line on the ozone figure gives the
extent of the vortex
71 Chemistry of the Atmosphere
(vi) The removal of nitric acid (and other oxides of nitrogen), by slow,
gravitational settling means that the reservoir species cannot be
regenerated. The HNO
3
is liberated within the particle.
In more recent times, there have been discoveries of ozone depletion in
the Arctic that occur by similar mechanisms as the ones described here
(see Figure 28). The Arctic equivalent does not tend to be as dramatic
owing to the fact the Artic stratosphere does not get as cold as the
Antarctic, mainly owing to a less well-formed vortex, largely owing to
northern hemisphere topography.
52
2.11 SUMMARY
The chemistry of the atmosphere is diverse, driven in the main by the
interaction of light with a few molecules that drives a complex array of
chemistry. The type and impact of atmospheric chemistry varies in
concert with the physical and biological change throughout the atmos-
phere. An integral understanding of atmospheric chemistry within the
earth system context underpins many contemporary global environmen-
tal problems and is therefore vital to sustainable development.
This chapter has outlined the main features of the chemistry of the
troposphere and stratosphere. In some senses it must be remembered
that our understanding of atmospheric chemistry is still evolving, but the
science expressed gives entry into the rich and changing world of
atmospheric science. In the coming years we need to understand the
interaction of atmospheric chemistry with climate as well as better
understand the multi-phase impacts of the chemistry. There is still much
to discover, rationalise and understand in atmospheric chemistry.
QUESTIONS
(i) The earth system is made up of the atmosphere, hydrosphere,
lithosphere and biosphere. Describe, with examples, the chem-
ical interactions between these different elements of the earth
system.
(ii) The amount of any chemical substance in the atmosphere is
dependent on the source–transport–sink relationship for that
compound. Describe the different types of sources of trace gases
in the atmosphere.
(iii) Discuss the following statement: ‘‘The atmosphere can be split
into different regions according to different physical or chemical
properties’’.
72 Chapter 2
(iv) Explain the following statement: ‘‘Ozone can be photolysed
both in the troposphere and stratosphere leading to quite
different chemistry’’.
(v) Why is the stratosphere separate from the troposphere?
(vi) Discuss the chemistry of ozone in the stratosphere in terms of
the relationships between catalytic species and the different
types of reservoir chemistry.
(vii) Explain the main chemical and physical features of the so-called
ozone ‘‘hole’’.
(viii) The hydroxyl radical (OH) has different role in the stratosphere
and troposphere. Give an example of the reactions of OH in
troposphere and stratosphere and describe their significance.
(ix) What role does the boundary layer play in the mixing of gases?
(x) What are the main reactions that contribute to the formation of
the so-called photochemical smog?
(xi) What physical, chemical and social effects can aggravate the
formation of photochemical smog?
(xii) Peroxyacetylnitrate (PAN) is of interest as a characteristic
product of tropospheric photochemistry.
(i) How is PAN formed in the atmosphere?
(ii) The unimolecular decomposition of PAN to peroxy acetyl
radicals and NO
2
is strongly temperature dependent. The
following expression gives the temperature dependence of
the unimolecular rate constant:
k ¼ 1:0 Â10
17
exp À
14; 000
T

:
If the lifetime is given by 1/k, calculate the atmospheric
lifetime of PAN at T¼310, 298, 290 and 280 K.
(iii) In the light of your answer to part (b), comment on the
potential of PAN as a reservoir for reactive nitrogen in
remote regions.
(xiii) Explain the following:
(i) In the shadow of a thick cloud the concentration of OH falls
to nearly zero.
(ii) On a global scale the concentration distribution of CO
2
is
about the same whereas the concentration of isoprene varies
from one location to the next.
(iii) There is more than one chemical pathway to the initiation
of night-time chemistry.
73 Chemistry of the Atmosphere
(iv) Both HONO and HCHO are detected in abundance in
areas suffering from photochemical smog and may lead to
the acceleration of the production of smog.
(v) The effect that NO
x
from aeroplanes and lightning can have
on ozone can be quite different from NO
x
emitted from the
surface of the earth.
(xiv) The figure below shows two sets of ozone profiles taken over
Halley Bay in Antarctica during Winter/Spring.
(i) What measurement platforms are normally used to take an
ozone profile?
(ii) Why under normal conditions (August 15
th
) is the ozone
maximum at 20 km?
(iii) Describe the key processes that have contributed to the loss
of ozone by October 13
th
.
(iv) What molecules are thought to be responsible for the ozone
loss shown in the figure?
(xv) The ozone continuity equation below is a reasonable represen-
tation of the processes that controls ozone in the boundary
layer, viz
74 Chapter 2
d½O
3
Š
dt
¼ C þ
E
v
ð½O
3
Š
ft
À½O
3
ŠÞ
H
þ
v
d
½O
3
Š
H
C is a term representative of the photochemistry (production or
destruction), E
v
the entrainment velocity, [O
3
]
ft
the concentra-
tion of free tropospheric ozone, v
d
the dry deposition velocity
and H the height of the boundary layer. The ozone budget
shown in Table 8 has been calculated both in the summer and
winter using the ozone continuity equation for a site in the
marine boundary layer.
(i) Describe the chemistry involved in calculating the term C
in the ozone continuity equation.
(ii) Given the magnitude of the photochemical terms in Table 8,
comment on the amount of available NO
x
.
(iii) How does the ability to make or destroy ozone change with
season?
(iv) What factors affect the magnitude of a deposition velocity?
(v) What role does entrainment play in the boundary layer?
(vi) What are the weaknesses of using this approach for the
calculation of chemical budgets?
(vii) Predict the likely diurnal cycle of ozone and hydrogen
peroxide in the remote marine boundary layer.
(xvi) Nitric acid has many potential loss processes in the troposphere.
Given that the reaction
OHþHNO
3
!H
2
OþNO
3
has a rate constant of 2.0 Â 10
À13
cm
3
molecule
À1
s
À1
and the
hydroxyl radical concentration is 4 Â 10
6
molecule cm
À3
. The
Table 8 Calculated average ozone removal and addition rates according to
pathway, ppbv day
À1
(upper part) and fractional contributions to
overall production or destruction patyways (lower part)
Pathway
O
3
removal O
3
addition
Photochemistry
(%)
Deposition
(%)
Photochemistry
(%)
Entrainment
(%)
Summer 1.19 0.18 0.56 2.1
Winter 0.61 0.35 0.29 0.1
Summer 87 13 21 79
Winter 64 36 74 26
75 Chemistry of the Atmosphere
deposition velocity for HNO
3
is 0.005 cm s
À1
over a 1 km well-
mixed boundary layer and the photoprocess data given in Table 9.
What is the atmospheric lifetime of HNO
3
?
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61. P.S. Monks, A.R. Rickard, S.L. Hall and N.A.D. Richards, J.
Geophys. Res., 2004, 109, D17206.
62. P.D. Lightfoot, R.A. Cox, J.N. Crowley, M. Destriau, G.D. Hay-
man, M.E. Jenkin, G.K. Moortgat and F. Zabel, Atmos. Environ.,
1992, 10, 1805.
63. D. Lamb, D.F. Miller, N.F. Robinson and A.W. Gertler, Atmos.
Environ., 1987, 21, 2333.
64. U. Frieß, Spectroscopic measurements of atmospheric trace gases at
Neumayer station, Antarctica, Ph.D. Thesis, University of Heidelb-
erg, Germany, 2001.
65. WMO, Scientific assessment of ozone depletion: 1998, Global
Ozone Research and Monitoring Project, Report No. 44, Geneva,
1999.
79 Chemistry of the Atmosphere
CHAPTER 3
Chemistry of Freshwaters
MARGARET C. GRAHAM AND JOHN G. FARMER
School of GeoSciences, University of Edinburgh, Crew Building, King’s
Buildings, West Mains Road, Edinburgh EH9 3JN
3.1 INTRODUCTION
Water is essential for all life on Earth. As the Earth’s population
continues to increase rapidly, the growing human need for freshwater
(e.g. for drinking, cooking, washing, carrying wastes, cooling machines,
irrigating crops, receiving sewage and agricultural runoff, recreation, and
industrial purposes) is leading to a global water resources crisis. Rees
1
has
commented that ‘there is a growing consensus that if current trends
continue, water scarcity and deteriorating water quality will become the
critical factors limiting future economic development, the expansion of
food production, and the provision of basic health and hygiene services to
millions of disadvantaged people in developing countries’. In 2003, the
UN International Year of Freshwater, 20% of the world’s people lacked
good drinking water and 40% lacked adequate sanitation facilities.
2
The inventory of water at the Earth’s surface (Table 1)
3
shows that the
oceans, ice caps, and glaciers contain 98.93% of the total, with ground-
water (1.05%) accounting for most of the rest, and lakes and rivers
amounting to only 0.009% and 0.0001%, respectively.
3
The average
annual water withdrawal for use by humans is currently about 4000
km
3
, of which 69% is used by agriculture, 21% by industry/power, and
10% for domestic purposes.
2
Figures vary widely between continents and
countries. On a per capita basis, North America withdraws seven times as
much freshwater as Africa. The USA (41% agriculture, 46% industry/
power, 13% domestic) withdraws almost 20% of its renewable freshwater
resources each year, in comparison with 7% for the UK (3%, 75%, 22%),
22% for China (68%, 26%, 7%), 33% for Poland (8%, 79%, 13%), 51%
80
for India (86%, 5%, 8%), and 76% for Bangladesh (96%, 1%, 3%).
2
Many developing countries are using up to 40% of their renewable
freshwater for irrigation.
2
As a consequence of population growth,
pollution and climate change, the average supply of water per person is
likely to drop by one-third over the next two decades,
4
with a global
supply crisis projected to occur between 2025 and 2050, although much
earlier for some individual countries.
1,2,4
The quality of freshwater is also of concern. For example, about 75%
of Europe’s drinking water is taken from groundwater,
2
a resource
described as overexploited in almost 60% of European industrial and
urban centres and threatened by pollutants.
5
River and lake eutrophica-
tion caused by excessive phosphorus and nitrogen from agricultural,
domestic, and industrial effluents is a problem across most of Europe.
The Eastern European countries in particular fare badly when judged
against the criteria of pathogenic agents, organic matter, salinization,
nitrate, phosphorus, heavy metals, pesticides, acidification, and radio-
activity, and even the Nordic countries of Norway, Sweden, and Fin-
land, despite having generally better freshwater conditions than the rest
of Europe, suffer from acidification.
5
In Asia, 86% of all urban waste-
water and 65% of all wastewater is discharged, untreated, into the
aquatic environment.
6
There is also the unexpected and insidious
chemical contamination of apparently clean drinking water supplies,
exemplified most notably by the arsenic contamination of groundwater
that affects millions in Bangladesh and other Asian countries.
2
Table 1 Inventory of water at the Earth’s surface
Reservoir Volume 10
6
km
3
(10
18
kg) Per cent of total
Oceans 1400 95.96
Mixed layer 50
Thermocline 460
Abyssal 890
Ice caps and glaciers 43.4 2.97
Groundwater 15.3 1.05
Lakes 0.125 0.009
Rivers 0.0017 0.0001
Soil moisture 0.065 0.0045
Atmosphere total
a
0.0155 0.001
Terrestrial 0.0045
Oceanic 0.0110
Biosphere 0.002 0.0001
Approximate total 1459
Source: Global Environment: Water Air Geochemical Cycles by Berner/Berner, r 1996.
Adapted by permission of Prentice-Hall, Upper Saddle River, NJ.
3
a
As liquid volume equivalent of water vapour.
81 Chemistry of Freshwaters
The effects of contaminants or pollutants on freshwater depend upon
their chemical, physical, and biological properties, their concentrations
and duration of exposure. Aquatic life may be affected indirectly (e.g.
through depletion of oxygen caused by biodegradation of organic matter)
or directly, through exposure to toxic or carcinogenic chemicals, some of
which may accumulate in organisms. Such toxicity may, however, be
modified by the presence of other substances and the characteristics of the
particular water body. For example, metal toxicity is affected by pH,
which influences speciation; dissolved organic carbon has been shown to
reduce bioavailability by forming metal complexes and by subsequent
adsorption to particulate matter in freshwater.
7
The toxicity of many
heavy metals to fish is also inversely related to water hardness, with Ca
21
competing with free metal ions for binding sites in biological systems.
In biologically productive lakes which also develop a thermocline in
summer, the bottom water may become depleted in oxygen, leading to a
change from oxidizing to reducing conditions. As a result, the potential
exists for remobilization of nutrients and metals from bottom sediments
to the water column, one more example of how alterations in master
variables in the hydrological cycle, in this case the redox status, can
affect the fate and influence of pollutants.
A further demonstration of the importance of fundamental properties of
both pollutants and water bodies is provided by the behaviour of chemicals
upon reaching a groundwater aquifer. Soluble chemicals, such as nitrate,
move in the same direction as groundwater flow. A poorly soluble liquid
which is less dense than water, such as petrol, spreads out over the surface
of the water table and flows in the direction of the groundwater. Poorly
soluble liquids which are denser than water, such as various chlorinated
solvents, sink below the water table and may flow separately along low
permeability layers encountered at depth in the aquifer and not necessarily
in the same direction as that of the overlying groundwater.
7
The rest of this chapter therefore consists of two major sections, first
on fundamental aquatic chemistry of relevance to the understanding of
pollutant behaviour in the aquatic environment and second on asso-
ciated case studies and examples drawn from around the world, includ-
ing reference to water treatment methods where appropriate.
3.2 FUNDAMENTALS OF AQUATIC CHEMISTRY
3.2.1 Introduction
3.2.1.1 Concentration and Activity. All natural waters contain dis-
solved solutes. In order to understand their chemical behaviour in
82 Chapter 3
aqueous systems, it is first necessary to consider the relationship between
solute concentration and solute activity.
The activity of a solute is a measure of its observed chemical
behaviour in (aqueous) solution. Interactions between the solute and
other species in solution lead to deviations between solute activity {i} and
concentration [i]. An activity coefficient, g
i
, is therefore defined as a
correction factor, which interrelates solute activity and concentration.
{i} ¼ g
i
[i] (3.1)
Concentration and activity of a solute are only the same for very dilute
solutions, i.e. g
i
approaches unity as the concentration of all solutes
approaches zero. For non-dilute solutions, activity coefficients must be
used in chemical expressions involving solute concentrations.
w
Although
freshwaters are sufficiently dilute to be potable (containing less than
about 1000 mg L
À1
total dissolved solids (TDS)),
8
it cannot be assumed
that activity coefficients are close to unity.
Calculation of activities using the expression in Equation (3.1) would
appear to be straightforward, requiring only a value for the activity
coefficient and the concentration of the solute, i. The activity coefficients
for individual ions, g
i
, cannot, however, be measured. The presence of
both cations and anions in solution means that laboratory experiments
quantifying either the direct (e.g. salt solubility) or indirect (e.g. elevation
of boiling point, depression of freezing point, etc.) effects of the presence
of solutes in aqueous solution generally lead to the mean ion activity
coefficients, g
Æ
. Traditionally, single-ion activity coefficients have been
obtained from the mean values, e.g. using the mean-salt method (Example
3.1),
9,10
but this approach has been shown to be inadequate because it
ignores ion pairing effects at higher solute concentrations.
11,12
This is
generally more significant for anions than for cations because the extent
of anion association at higher solute concentration is much greater.
13
Example 3.1: Determination of single-ion activity coefficients for Ca
21
from mean values for CaCl
2
using the mean-salt method.
The solubility of calcium chloride in water can be expressed as
CaCl
2(s)
"Ca

(aq)
þ 2Cl
À
(aq)
K
SP
w
Concentration is expressed on the molar scale in terms of mol L
À1
of solvent or on the molal scale
in terms of mol kg
À1
of solvent. The molal scale gives concentrations that are independent of
temperature and pressure. In this chapter, the molar scale will be used on the basis that molarity
and molality are almost identical for the low ionic strengths commonly associated with fresh-
waters.
83 Chemistry of Freshwaters
where the solubility product,
K
SP
¼ Ca

È É
Cl
À
f g
2
¼ g
Ca
2þg
2
Cl
À ½Ca

Š½Cl
À
Š
2
We define the mean ion activity coefficient as the geometric mean of
the single-ion activity coefficients
g
ÆCaCl
2
¼ ðg
Ca
2þg
Cl
Àg
Cl
ÀÞ
1=3
The mean ion activity coefficient values can be obtained from experi-
ments where the effect of electrolyte concentration on the K
SP
value
for a salt is determined. The mean values are then compared with
those for KCl under the same solution conditions. The single-ion
activity coefficient for Ca
21
can then be computed if an assumption is
made about the individual values for K
1
and Cl
À
. These ions have the
same magnitude of charge and similar electronic configuration, ionic
radii, and ionic mobilities. On the basis of these properties, the
MacInnes convention (1919) states that
g
K
1
¼ g
Cl
À
¼ g
ÆKCl
In general: g
cation
¼ ðg
ÆcationCl
xÀ1
Þ
x
=ðg
ÆKCl
Þ
xÀ1
Thus g
ÆCaCl
2
¼ ðg
Ca
2þg
2
Cl
ÀÞ
1=3
¼ ðg
Ca
2þg
2
ÆKCl
Þ
1=3
and g
Ca
2þ ¼ ðg
ÆCaCl
2
Þ
3
=ðg
ÆKCl
Þ
2
For I ¼ 0.1 mol l
À1
: g
Ca
2þ ¼ ð0:518Þ
3
=ð0:770Þ
2
¼ 0:234
(Mean salt data from Robinson and Stokes.
9
)
Although other methods using such experimental data have been
documented,
14
theoretical and/or empirical considerations have led to
various expressions involving a dependence on ionic strength, I, which is
a major factor influencing the activity of solutes in aqueous solution.
3.2.1.2 Ionic Strength. Ionic strength, I, is a measure of the charge
density in solution and is defined as
I ¼ 0:5
X
i
i ½ Šz
2
i
À Á
ð3:2Þ
84 Chapter 3
where [i] is the concentration of solute ion, i; z
i
is the integral charge
associated with solute ion, i.
Ionic strength, expressed in terms of mol L
À1
, is most accurately
determined by carrying out a total water analysis, i.e. quantification of
the concentrations of all ionic species in solution and calculation of I
using Equation (3.2). It may, however, be estimated from measurements
of either the TDS in solution or, preferably, the specific conductance
(SpC) of the solution, e.g. I ¼ 2.5 Â 10
À5
TDS (mg L
À1
) or I ¼ 1.7 Â
10
À5
SpC (mS cm
À1
).
12
The simplest theoretical relationship between I and g
i
is expressed in the
Debye–Hu¨ ckel (DH) Equation (3.3).
z
The DH model assumes that ions
can be represented as point charges, i.e. of infinitely small radius, and that
long-range coulombic forces between ions of opposite charge are respon-
sible for the differences between the observed chemical behaviour,
i.e. activity, and the predicted behaviour on the basis of solute concent-
ration.
log g
i
¼ À0:5 z
2
i
I
p
DH equation ð3:3Þ
log g
i
¼ À0:5 z
2
i
I
p
= 1 þ 0:33 a
i
I
p À Á À Á
Extended DH equation ð3:4Þ
log g
i
¼ À0:5 z
2
i
I
p
= 1 þ I
p À Á À Á
G ¨ untelberg approximation ð3:5Þ
An infinitely dilute solution is defined as having an ionic strength o10
À5
mol L
À1
and activity coefficients calculated by any of the above
equations would have a value of unity. For freshwaters where I is in
the range 10
À5
–10
À2.3
mol L
À1
, activity coefficients can be calculated
using the DH Equation (3.3). Where I is in the range 10
À2.3
–10
À1
mol
L
À1
, however, the values calculated using Equation (3.3) differ from
experimental data and this stems from the assumption that the solute
ions are point charges. The extended DH expression (3.4) includes a
parameter, a
i
, which is related to ion size. Example 3.2 illustrates the use
of both DH and extended DH expressions to calculate single-ion activity
coefficients.
z
The general forms of the DH and extended DH equations are log g
i
¼ ÀAz
i
2
OI and log g
i
¼
ÀAz
i
2
(OI/(1 þ Ba
i
OI)), respectively, where A and B are temperature dependent constants. A ¼
1.824928 Â 10
6
r
0
0.5
(eT)
À1.5
B0.5 and B ¼ 50.3 (eT)
À0.5
B0.33 at 298 K, where r
0
is the density
and e is the dielectric constant of water at 298 K.
85 Chemistry of Freshwaters
Example 3.2: Calculation of single-ion activity coefficients using the
DH and extended DH equations.
If a solution contains 0.01 mol L
À1
MgSO
4
, 0.006 mol L
À1
Na
2
CO
3
,
and 0.002 mol L
À1
CaCl
2
then the ionic strength of solution is
I ¼0:5ð0:01 Â ðþ2Þ
2
þ 0:01  ðÀ2Þ
2
þ 0:006 Â 2 Â ðþ1Þ
2
þ 0:006  ðÀ2Þ
2
þ 0:002 Â ðþ2Þ
2
þ 0:002  2  ðÀ1Þ
2
Þ
¼ 0:5ð0:04 þ 0:04 þ 0:012 þ 0:024 þ 0:008 þ 0:004Þ
¼ 0:064mol L
À1
Calculating the single-ion activity coefficient for Na
1
using both the
DH and the extended DH equations (use a value of 4.5 for the ion size
parameter, a
i
)
DH log g
Na
þ ¼ À 0:5ðþ1Þ
2
ð
p
0:064Þ ¼ À0:126 g
Na
þ ¼ 0:747
Ex-DH log g
Na
þ ¼ À 0:5ðþ1Þ
2
ð
p
0:064Þ
= 1 þ 0:33 Â 4:5 Â ð
p
0:064Þ ð Þ
¼ À 0:0919 g
Na
þ ¼ 0:809
At I ¼ 0.064 mol L
À1
, the single-ion activity coefficient calculated by the
DHmodel is B8%lower than that calculated by the extended DHmodel.
Now consider a solution which has an ionic strength of only 0.001
mol L
À1
.
DH log g
Na
þ ¼ À 0:0158 g
Na
þ ¼ 0:964
Ex À DH log g
Na
þ ¼ À 0:0151 g
Na
þ ¼ 0:966
Clearly, at lower ionic strength, the single-ion activity coefficient is much
closer to unity. Also, the DH and the extended DH models give almost
exactly the same value. This is because the denominator (1þ0.33a
i
OI) of
the extended DH equation approaches a value of unity, i.e. 0.33a
i
OI
approaches zero, as the ionic strength decreases towards zero. In other
words, the two equations become identical at very low ionic strength.
It should be noted that, for solutions of ionic strength o10
À1
mol
L
À1
, either Equation (3.4) or the Gu¨ ntelberg approximation (3.5), which
incorporates an average value of 3 for a
i
, can be used.
13
The Gu¨ ntelberg
approximation is particularly useful in calculations where a number of
ions are present in solution or when values of the ion size parameter are
poorly defined.
86 Chapter 3
For solutes in higher ionic strength solutions, however, Equations
(3.3)–(3.5) tend to underestimate activity coefficients in part because of
the assumptions that are inherent in the DH and extended DH Equations,
e.g. only long-range coulombic interactions, ion size parameters are
independent of ionic strength, ions of like charge do not interact, each
ion can construct its own atmosphere of ions of opposite charge.
8,12,15,16
Additional factors are that (i) short-range interactions (including those
between ions of like charge and also between ions and neutral mole-
cules),
12,15–17
rather than the long-range coulombic interactions, between
ions become increasingly important and (ii) the number of water mole-
cules involved in ion hydration spheres means that the activity of water
decreases to a value significantly less than unity.
12
In order to compensate
particularly for the effect of (ii), various empirical correction factors have
subsequently been added to the extended DH expression.
log g
i
¼ À0:5 z
2
i
I
p
= 1 þ 0:33 a
i
I
p À Á
À bI
À Á
Truesdell ÀJones equation ð3:6Þ
log g
i
¼ À0:5 z
2
i
I
p
= 1 þ I
p À Á
À bI
À Á
Davies equation ð3:7Þ
The Truesdell–Jones
18
equation contains an empirical term, bI, as well as
the ion size parameter, a
i
. Values of both a
i
and b are often obtained by
fitting this equation to the individual activity coefficients obtained from
mean salt data using the MacInnes convention (see Example 3.1).
9,10
This
equation is used in some geochemical computer models, e.g.
PHREEQE.
19
The Davies equation, which also incorporates an empirical
term bI but uses an average ion size parameter (a
i
¼ 3), is more commonly
used because the ion size parameter is not well defined for all ions. The
Davies equation can be used to calculate activity coefficients for mono-
valent and divalent ions in aqueous solutions, where I ¼ 0.1–0.7 mol L
À1
and I ¼ 0.1–B0.3 mol L
À1
, respectively. Originally, Davies used a value
of 0.2 for b but later suggested that the value be increased to 0.3.
20,21
The
geochemical computer model MINTEQA2 employs the Davies equation
to calculate single-ion activity coefficients but uses a value of 0.24 for b.
22
Specific Ion Interaction Theory (SIT) is a more advanced empirical
approach that was developed by Guggenheim
23
and extended by
Scatchard and others.
24–26
The SIT equation has an extended DH term
that accounts for the non-specific long-range interactions but also has an
ion- and electrolyte-specific correction factor, e
ij
[j], for each pair of ions,
i and j, of opposite charge. Brønsted
27
also recognized the importance of
short-range interactions in higher ionic strength solutions and Equation
(3.8) is often referred to as the Brønsted–Guggenheim equation.
log g
i
¼ ‘Extended DH’ þ S
j
e
ij
[j] (3.8)
87 Chemistry of Freshwaters
Originally the extended DH term was similar to that in Equation (3.5),
i.e. with an average ion size parameter, a
i
¼ 3. Scatchard
28
showed that a
better fit with experimental data was obtained using an average value of
a
i
¼ 4.6, i.e. 0.33a
i
¼ 1.5, and so the extended DH expression used in the
SIT model is often
log g
i
¼ À0:510 z
2
i
I
p
= 1 þ 1:5 I
p À Á
ð3:9Þ
Overall, however, the SIT approach is limited in application to inter-
mediate ionic strength solutions (0.1–3.5 mol L
À1
).
The Pitzer model can be used to obtain activity coefficients for solutes
in low (o0.1 mol L
À1
), intermediate (0.1–3.5 mol L
À1
) and high (43.5
mol L
À1
) ionic strength solutions. The Pitzer equations
29
include terms
for binary and ternary interactions between solute species as well as a
modified DH expression. The general formula is
ln g
i
¼ z
2
i
f
g
þ
X
j
D
ij
½jŠ þ
X
jk
E
ijk
½jŠ½kŠ þ . . . ð3:10Þ
where f
g
is the modified DH term
f
g
¼ À0.392 (OI/(1 þ 1.2OI) þ (2/1.2) ln(1 þ 1.2 OI)) (3.11)
and the D
ij
terms describe interactions between pairs of ions, i and j,
while the E
ijk
terms describe interactions among three ions, i, j, and k.
Higher-order terms can also be added to this general formula. A key
difference between the SIT and Pitzer models is that interactions
between ions of like charge are also included. For ionic strength
solutions of up to B3.5 mol L
À1
, there is good agreement between the
two models but, at 43.5 mol L
À1
, the ternary and higher-order terms in
the Pitzer equations become more important and this model gives the
more accurate ion activity coefficients.
12
Although naturally occurring brines and some high ionic strength
contaminated waters may require the more complicated expressions
developed in the Davies, SIT, or Pitzer models, the use of Equations
(3.3)–(3.5) is justified for the ionic strengths of many freshwaters.
Finally, this section has focused primarily on ions in aqueous solution
but it should be remembered that aqueous solutions also contain
important dissolved neutral species, e.g. O
2
, CO
2
, H
2
CO
3
, Si(OH)
4
.
For non-ideal solutions, the Setschenow Equation (1899) has tradition-
ally been used to describe the ionic strength dependence of the activity
coefficients for dissolved neutral species and can be written as
log g
i
¼ k
i
[i] (3.12)
88 Chapter 3
where k
i
is the temperature dependent salting out coefficient for mole-
cular species, i.
At higher ionic strength values, an additional dependence on [i]
2
is often
required to fit the observed solubility data.
17
Alternatively, the Pitzer
model can be used with a high degree of accuracy to describe the short-
range binary (neutral–neutral, neutral–cation, neutral–anion) and ternary
(neutral–neutral–neutral, neutral–cation–anion) interactions between ions
and neutral species in single and mixed electrolyte solutions.
17
3.2.1.3 Equilibria and Equilibrium Constants. Many of the important
reactions involving solutes in freshwaters can be described by equilibria.
This approach means that an equilibrium constant, K, relating the
activities of the solutes, can be defined for each stoichiometric equili-
brium expression.
a A þ b B "c C þ d D (3.13)
K ¼ {C}
c
{D}
d
/ {A}
a
{B}
b
(3.14)
The equilibrium constant can also be defined in terms of the concentra-
tions of the solutes.
K ¼ (g
c
[C])
c
(g
d
[D])
d
/(g
a
[A])
a
(g
b
[B])
b
(3.15)
For infinitely dilute solutions, { } ¼ [ ] and the equilibrium constant can
be written as
K ¼ [C]
c
[D]
d
/[A]
a
[B]
b
(3.16)
For solutions of fixed ionic strength, or, for example, where major ions
in solution, e.g. conservative cations and anions, are present at concen-
trations several orders of magnitude greater than the species involved in
the chemical equilibrium, e.g. A, B, C, and D in Equation (3.13), it can
be assumed that the solute activity coefficients are also constants and
can be incorporated into the equilibrium constant. The equilibrium
constant for a fixed ionic strength aqueous solution is termed a constant
ionic strength equilibrium constant,
c
K.
c
K ¼ [C]
c
[D]
d
/[A]
a
[B]
b
where
c
K ¼ (g
a
a
g
b
b
/ g
c
c
g
d
d
) K (3.17)
This again enables the use of concentrations rather than activities in
equilibrium calculations.
It is sometimes advantageous to use a mixture of activities and
concentrations and a mixed equilibrium constant, K
0
, is defined as
K
0
¼ {C}
c
[D]
d
/ [A]
a
[B]
b
where K
0
¼ (g
a
a
g
b
b
/ g
d
d
) K (3.18)
89 Chemistry of Freshwaters
For example, a mixed acidity constant is frequently used where pH has
been measured according to the IUPAC convention as the activity of
hydrogen ions but the concentrations of the conjugate acid-base pair are
used.
The relationship between K and
c
K or K and K
0
as defined above can
be used to calculate the effect of ionic strength of solution on the true
equilibrium constant, K.
c
K and K
0
can be calculated using the Equa-
tions (3.3)–(3.5) together with experimentally determined values of K
(Example 3.3).
Example 3.3: Calculation of the mixed acidity constant, K
0
, using the
Gu¨ntelberg approximation and the Davies equation.
For an acid-base equilibrium:
HA "H
1
þ A
À
K ¼ {H
1
}{A
À
}/{HA}
K
0
¼ ðg
HA
=g
A
ÀÞ K
Taking logs:
logK
0
¼ log g
HA
=g
A
À ð Þ þ log K
pK
0
¼ pK þ log g
A
À À log g
HA
Using the Gu¨ ntelberg approximation:
pK
0
¼ pK þ 0:5 z
2
HA
À z
2
A
À
À Á
I
p
= 1 þ I
p À Á À Á
Using the Davies equation:
pK
0
¼ pK þ 0:5 z
2
HA
À z
2
A
À
À Á
I
p
= 1 þ I
p À Á
À 0:3I
À Á
Now calculate the mixed acidity constant, K
0
, at ionic strength values
of (i) 0.05 mol L
À1
using the Gu¨ ntelberg approximation and (ii) 0.4 mol
L
À1
using the Davies equation for a monoprotic acid, HA, with K ¼
6.8 Â 10
À8
:
(i)
pK
0
¼ 7:17 þ 0:5 ð0 À ð À 1Þ
2
Þ ð 0
p
:05=ð1 þ 0
p
:05ÞÞ
¼ 7:17 À 0:0914 ¼ 7:08
K
0
¼ 8:34 Â 10
À8
90 Chapter 3
(ii)
pK
0
¼ 7:17 þ 0:5ð0 À ð À 1Þ
2
Þ ð 0
p
:4=ð1 þ 0
p
:4Þ À 0:3 Â 0:4Þ
¼ 7:17 À 0:5 ð0:387 À 0:12Þ ¼ 7:04
K
0
¼ 9:19 Â 10
À8
The values for the corrected constants, K
0
, are 22% and 35% greater,
respectively, than the infinite dilution constant, K.
At higher ionic strengths, the activity coefficients could be calculated
using the SIT or Pitzer equations and thus a more accurate correction
made to the infinite dilution constant, K.
Finally, it should be noted that all values of the equilibrium constants
apply only at a specified temperature. In Sections 3.2.2–3.2.4, the values
of the equilibrium constants apply at 298 K unless stated otherwise.
3.2.2 Dissolution/Precipitation Reactions
Section 3.2.1 has provided relationships between solute activities and
concentrations in solution in order that solute behaviour can be
quantified. This section discusses dissolution and precipitation reactions
that impart or remove solutes to/from natural waters, and therefore
modify the chemical composition of natural waters.
3.2.2.1 Physical and Chemical Weathering Processes. Initial steps
involving physical weathering by thermal expansion and contraction
or abrasion lead to the disintegration of rock. Disintegration increases
the surface area of the rock, which, in the presence of water, can undergo
chemical weathering. Water acts not only as a reactant but also as a
transporting agent of dissolved and particulate components, and so
weathering processes are extremely important in the hydrogeochemical
cycling of elements. Mineral dissolution reactions often involve hydro-
gen ions from mineral or organic acids, e.g. acid hydrolysis of Na-
feldspar in Equation (3.21). Alternatively, the transfer of electrons
(sometimes simultaneously with proton transfer) may promote the
dissolution of minerals, e.g. reductive dissolution of biotite.
Chemical weathering of minerals results not only in the introduction
of solutes to the aqueous phase but often in the formation of new solid
phases. Dissolution is described as congruent, where aqueous phase
solutes are the only products, or incongruent, where new solid phase(s)
in addition to aqueous phase solutes are the products. These reactions
91 Chemistry of Freshwaters
can be represented by equilibria, where the equilibrium constant is
related only to the activities of the aqueous solutes, i.e. an assumption
is made that the activities of solid phases have the value of unity.
Examples of weathering of primary minerals, those formed at the same
time as the parent rock, are shown in (3.19)–(3.22):
Congruent dissolution of quartz
SiO
2ðsÞ
þ 2 H
2
O Ð SiðOHÞ
0
4ðaqÞ
quartz silicic acid
ð3:19Þ
K ¼ {Si(OH)
4
0
} (3.20)
At pHo9, the equilibrium between quartz and silicic acid can be
represented as in (3.19) and the value of K at 298 K is 1.05 Â 10
À4
mol L
À1
,
30
indicating that the solubility of quartz is low. At higher pH
values, the dissociation of silicic acid results in the increased solubility of
quartz (see Section 3.2.4.1).
Incongruent dissolution of Na-feldspar
2 NaAlSi
3
O
8ðsÞ
Na-feldspar
þ2 H
þ
þ 9 H
2
O ÐAl
2
Si
2
O
5
ðOHÞ
4ðsÞ
kaolinite
þ2 Na
þ
ðaqÞ
þ 4 SiðOHÞ
0
4ðaqÞ
silicic acid
ð3:21Þ
K ¼ fSiðOHÞ
0
4
g
4
fNa
þ
g
2
=fH
þ
g
2
ð3:22Þ
Alteration of primary minerals such as the feldspars gives rise to
secondary minerals such as kaolinite (Al
2
Si
2
O
5
(OH)
4
), smectites (e.g.
Na
0.33
Al
2.33
Si
3.67
O
10
(OH)
2
), and gibbsite (Al(OH)
3
). As the composition
of the new mineral phases and the potential for further alteration of
secondary minerals are a function of the prevailing geochemical condi-
tions, many equilibrium expressions must be used to fully describe
chemical weathering processes in natural systems. For example, reac-
tions leading to the formation of kaolinite from the primary mineral,
Na-feldspar, as well as alteration of the secondary mineral, e.g. to
gibbsite, must be considered. The composition of the aqueous phase is
of major importance in determining the nature of the solid products
formed during chemical weathering. In particular, the solution activities
of silicic acid, metal ions, and hydrogen ions are key parameters
influencing the formation and alteration processes of new solid phases
(Example 3.4).
8
92 Chapter 3
Example 3.4: Investigation of the stability relationship between gibbsite
and kaolinite in natural waters at pHo7.
Consider the acid hydrolysis weathering reaction undergone by Na-
feldspars (pHo7):
NaAlSi
3
O
8(s)
þ H
þ
(aq)
þ 7H
2
O "Na
þ
(aq)
þ Al

(aq)
þ 3OH
À
(aq)
þ 3Si(OH)
4(aq)
This equilibrium expression represents congruent dissolution of Na-
feldspar but the solution quickly becomes saturated with respect to
the solid phase Al(OH)
3
(gibbsite K
SP
¼ 10
À33.9
) and so the secondary
mineral, gibbsite, is formed.
NaAlSi
3
O
8(s)
þ H
þ
(aq)
þ 7H
2
O "Al(OH)
3(s)
þ Na
þ
(aq)
þ 3Si(OH)
4(aq)
The concentration of silicic acid in solution is a key parameter
influencing the stability of gibbsite. In the presence of even low
concentrations of silicic acid, e.g. 10
À4
mol L
À1
, kaolinite would be
formed instead.
2NaAlSi
3
O
8(s)
þ 2H
þ
(aq)
þ 9H
2
O "Al
2
Si
2
O
5
(OH)
4(s)
þ 2Na
þ
(aq)
þ 4Si(OH)
4(aq)
In natural systems, the role of water as a transporting agent is
important. Geochemical conditions promoting removal of silicic acid
from the solid-water interface (e.g. water flow) favour the formation
of gibbsite over kaolinite.
(Adapted from Drever.
8
)
3.2.2.2 Solubility. Dissolution of minerals during chemical weath-
ering releases species into solution but aqueous phase concentrations
are limited by the solubility of solid phases, such as amorphous silica,
gibbsite, and metal salts. For example, the solubility of Al
III
and
Ca
II
may be limited by the formation of gibbsite and gypsum, respec-
tively.
Al(OH)
3 gibbsite
"Al

(aq)
þ 3OH
À
(aq)
(3.23)
CaSO
4
.2H
2
O
gypsum
"Ca

(aq)
þ SO
4

(aq)
þ 2H
2
O (3.24)
The equilibrium solubilities are defined by the respective solubility
products, K
SP
(values from ref. 30).
K
SP
¼ {Al
31
} {OH
À
}
3
¼ 10
À33.9
(3.25)
93 Chemistry of Freshwaters
K
SP
¼ {Ca
21
} {SO

4
} ¼ 10
À4.58
(3.26)
A solution is considered to be undersaturated, saturated, or oversaturated
with respect to a solid phase, for example gypsum, if K
SP
4
{Ca
21
}{SO
4

}
observed
, K
SP
¼ {Ca
21
}{SO
4

}
observed
, or K
SP
o{Ca
21
}
{SO
4

}
observed
, respectively.
3.2.2.3 Influence of Organic Matter. Natural organic matter is pre-
sent in most natural systems. With respect to weathering processes, its
importance in freshwaters and indeed soils and sediments in contact
with freshwaters can be attributed to the presence of organic acids,
which include low molecular weight compounds, e.g. oxalic acid, and
extremely complex, high molecular weight coloured compounds de-
scribed as humic substances – a heterogeneous mixture of polyfunctional
macromolecules ranging in size from a few thousand to several hundred
thousand Daltons (Da). In addition to inorganic acids, e.g. H
2
CO
3
,
these provide hydrogen ions for the acid hydrolysis of minerals. As well
as promoting dissolution, natural organic matter can influence the
formation of new mineral phases.
31
3.2.3 Complexation Reactions in Freshwaters
In this section, as a starting point, it is assumed that all species in
solution are in hydrated form, e.g. M
III
(H
2
O)

6
, where the six water
molecules form the first co-ordination sphere of the metal ion, M
III
. The
hydrated form is often represented as, for example, M

(aq)
.
3.2.3.1 Outer and Inner Sphere Complexes. Outer sphere complexa-
tion involves interactions between metal ions and other solute species in
which the co-ordinated water of the metal ion and/or the other solute
species are retained. For example, the initial step in the formation of ion
pairs, where ions of opposite charge approach within a critical distance
and are then held together by coulombic attractive forces, is described as
outer sphere complex formation.
Mg

(aq)
þ SO

4(aq)
"(Mg
21
(H
2
O)(H
2
O)SO

4(aq)
) (3.27)
The formation of ion pairs is influenced by the nature of the oppositely
charged ions, the ionic strength of solution, and ion charge. Ion pairs are
generally formed between hard (low polarizability) metal cations, e.g.
Mg
21
, Fe
31
, and hard anions, e.g. CO

3
, SO

4
, and ion pair formation
is generally most significant in high ionic strength aqueous phases. In
94 Chapter 3
freshwaters, which are frequently of low ionic strength, ion charge is a
key parameter. Greater coulombic interactions occur between oppo-
sitely charged ions with high charge.
Inner sphere complexation involves interactions between metal ions
and other species in solution which possess lone pairs of electrons. Inner
sphere complexation involves the transfer of at least one lone pair of
electrons. Those species which possess electron lone pairs are termed
ligands and reactions may involve inorganic or organic ligands.
3.2.3.2 Hydrolysis. In aqueous systems, hydrolysis reactions are an
important example of inner sphere complexation for many metal ions.
The interaction between hydrated metal ions and water can be written as
a series of equilibria for which the equilibrium constants are denoted
*K
n
.
y
Al

(aq)
þ H
2
O
(1)
"Al(OH)

(aq)
þ H
þ
(aq)
*K
1
¼ 10
À4.95
(3.28)
Al(OH)

(aq)
þH
2
O
(1)
"Al(OH)
þ
2(aq)
þ H
þ
(aq)
*K
2
¼ 10
À5.6
(3.29)
Al(OH)
þ
2(aq)
þH
2
O
(1)
"Al(OH)
3(aq)
þ H
þ
(aq)
*K
3
¼ 10
À6.7
(3.30)
Al(OH)
3(aq)
þH
2
O
(1)
"Al(OH)
À
4(aq)
þ H
þ
(aq)
*K
4
¼ 10
À5.6
(3.31)
Hydrolysis and, more generally, complex formation equilibria may be
described by cumulative stability constants, b
n
. Using the Equations
(3.28)–(3.31)
Al

(aq)
þH
2
O
(1)
"Al(OH)

(aq)
þ H
þ
(aq)
*b
1
¼ *K
1
¼ 10
À4.95
(3.32)
y
The hydrolysis of hydrated metal ions can also be written as the interaction between the hydrated
metal ion and the hydroxyl ligand. For example
Al
31
(aq)
þ OH
À
(aq)
"Al(OH)
21
(aq)
K
1
where K
1
and *K
1
are related as follows
Al
31
(aq)
þ OH
À
(aq)
"Al(OH)
21
(aq)
K
1
H
2
O
(l)
"H
1
(aq)
þ OH
À
(aq)
K
w
so
Al
31
(aq)
þ H
2
O
(l)
"Al(OH)
21
(aq)
þ H
1
(aq)
*K ¼ K
1
K
w
The values for *K
n
are those obtained by Wesolowski and Palmer;
32
all values are given in unitless
form but fundamentally are defined in terms of the products of the activities of ions on the molar or
molal scales.
95 Chemistry of Freshwaters
Al

(aq)
þ2H
2
O
(1)
"Al(OH)
þ
2(aq)
þ 2H
þ
(aq)
*b
2
¼ *K
1
*K
2
¼ 10
À10.55
(3.33)
Al

(aq)
þ3H
2
O
(1)
"Al(OH)
3(aq)
þ 3H
þ
(aq)
*b
3
¼ *K
1
*K
2
*K
3
¼ 10
À17.25
(3.34)
Al

(aq)
þ4H
2
O
(1)
"Al(OH)
À
4(aq)
þ 4H
þ
(aq)
*b
4
¼ *K
1
*K
2
*K
3
*K
4
¼ 10
À22.85
(3.35)
Clearly, these hydrolysis reactions are dependent on hydrogen ion
activity. The relationship between speciation and pH, which is influ-
enced by the characteristics of the metal ion, will be discussed further in
Section 3.2.4.1.
3.2.3.3 Inorganic Complexes. The main inorganic ligands in oxyge-
nated freshwaters, in addition to OH
À
, are HCO
3
À
, CO
3

, Cl
À
, SO
4

,
and F
À
, and, under anoxic conditions, HS
À
and S

(see Section 3.2.4.4).
The stability of complexes formed between metal ions and inorganic
ligands depends on the nature of the metal ion as well as the properties of
the ligand. Table 2 shows some of the major complexed metal species
involving inorganic ligands in oxygenated freshwaters at pH 8.
3.2.3.4 Surface Complex Formation. Metal ions form both outer and
inner sphere complexes with solid surfaces, e.g. hydrous oxides of iron,
manganese, and aluminium. In addition, metal ions, attracted to charged
surfaces, may be held in a diffuse layer, which, depending upon ionic
strength, extends several nanometres from the surface into solution.
Table 2 Major species in freshwaters
Metal ion Major species [M
x1
(aq)
]/[M
TOT (aq)
]
Mg
II
Mg
21
0.94
Ca
II
Ca
21
0.94
Al
III
Al(OH)
3
0
, Al(OH)
2
1
, Al(OH)
4
À
1 Â 10
À9
Mn
IV
MnO
2
0

Fe
III
Fe(OH)
3
0
, Fe(OH)
2
1
, Fe(OH)
4
À
2 Â 10
À11
Ni
II
Ni
21
, NiCO
3
0
0.4
Cu
II
CuCO
3
0
, Cu(OH)
2
0
0.01
Zn
II
Zn
21
, ZnCO
3
0
0.4
Pb
II
PbCO
3
0
0.05
Source: Adapted from Sigg and Xue,
33
and reproduced with permission from W. Stumm and J.J.
Morgan, Aquatic Chemistry 3rd Edn, r Wiley, 1996.
96 Chapter 3
Diffuse layer metal retention and outer sphere complex formation involve
electrostatic attractive forces, which are characteristically weaker than
co-ordinative interactions leading to inner sphere surface complex for-
mation. A number of factors influence metal interactions with surfaces,
including the chemical composition of the surface, surface charge, and
the nature and speciation of the metal ion. The importance of the pH
of the aqueous phase in these interactions will be discussed further in
Section 3.2.4.1.
3.2.3.5 Organic Complexes. Dissolved organic matter consists of a
highly heterogeneous mixture of compounds, including low molecular
weight acids and sugars as well as the high molecular weight coloured
compounds termed humic substances. Humic substances are secondary
synthetic products derived from decaying organic debris. Although they
are structurally poorly defined, it is accepted that large numbers of
mainly oxygen-containing functional groups are attached to a flexible,
predominantly carbon backbone. Individual organic molecules, in par-
ticular those of humic substances, can provide more than one functional
group for complex formation with a hydrated metal ion. Ligands which
provide two and three functional groups are termed bidentate and
tridentate, respectively. Complexes where more than one functional
group from the same organic molecule is involved are more stable than
those where functional groups are from discrete organic molecules. The
concentration of dissolved organic matter in freshwaters is generally low
(2–6 mg C L
À1
) and humic substances, comprising molecules which
possess large numbers of functional groups in numerous different
chemical environments, are implicated as the component of natural
organic matter most important in metal binding.
31
3.2.4 Species Distribution in Freshwaters
3.2.4.1 pH as a Master Variable. pH is one of the key parameters
which influences species distribution in aqueous systems. Many equili-
brium expressions contain a hydrogen ion activity term, e.g. acidity
constants, complexation constants. It is therefore useful to consider the
relationship between the activity of the species of interest (e.g. con-
taminant metal ions, organic pollutants, naturally occurring inorganic
and organic solutes, and weakly acidic functional groups on mineral
surfaces) and the activity of hydrogen ions. For example, an acid –
conjugate base pair can be represented as HA and A
À
, respectively.
HA "A
À
þ H
1
(3.36)
97 Chemistry of Freshwaters
K ¼ {A
À
}{H
1
}/{HA} (3.37)
The activity of acid initially in solution, C, termed the analytical activity,
is equal to the sum of the equilibrium activities of the acid and its
conjugate base.
C ¼ {HA} þ {A
À
} (3.38)
Equations (3.37) and (3.38) can be combined to give an expression for
the activity of the conjugate base in terms of the equilibrium constant, the
analytical activity, which is also a constant, and the hydrogen ion activity.
K ¼ {A
À
}{H
1
}/(CÀ{A
À
}) (3.39)
{A
À
} ¼ KC/(K þ {H
1
}) (3.40)
Similarly an expression for the activity of the acid can be written as
{HA} ¼ {H
1
}C/(K þ {H
1
}) (3.41)
Alternatively, the activities of acid and conjugate base can be repre-
sented as a fraction of the analytical activity.
a
0
¼ {HA}/C ¼ {H
1
}/(K þ {H
1
}) (3.42)
a
1
¼ {A
À
}/C ¼ K/(K þ {H
1
}) (3.43)
a
0
þa
1
¼ 1 (3.44)
a
0
and a
1
are termed dissociation fractions for the acid and conjugate
base, respectively. The expressions for the dissociation fractions are now
independent of the analytical activity.
A plot of dissociation fraction against pH for an acid-conjugate base
pair is shown in Figure 1.
More frequently, log{ } against pH is plotted using (3.45)–(3.46).
log {HA} ¼ log{H
1
} þ log C À log(K þ {H
1
}) (3.45)
log {A
À
} ¼ log K þ log C À log(K þ {H
1
}) (3.46)
The equilibrium pH can be obtained directly from the log{ } vs. pH plot
by adding lines showing log {H
1
} and log {OH
À
} and by using an
expression for charge balance.
{H
1
} ¼ {A
À
} þ {OH
À
} (3.47)
98 Chapter 3
For a solution containing a weak acid, the charge balance relationship
(3.47) is satisfied at the equilibrium pH (Example 3.5). The same log{ }
vs. pH plot can also be used to determine the equilibrium pH of a
solution containing the salt of a weak acid, e.g. NaA, by using the
appropriate charge balance expression.
{Na
1
} þ {H
1
} ¼ {A
À
} þ {OH
À
} (3.48)
Using C ¼ {Na
1
} ¼ {HA} þ {A
À
} gives
{HA} þ {H
1
} ¼ {OH
À
} (3.49)
Example 3.5: Graphical illustration of the relationship between (i)
log{2,4,6-TCP} and pH; (ii) log{2,4,6-TCP
À
} and pH for an organic
pollutant, 2,4,6-trichlorophenol (2,4,6-TCP), that has been released into a
natural water (assume I ¼ 0 mol L
À1
). Use C ¼ {2,4,6-TCP
TOTAL
} ¼ 4 Â
10
À4
mol L
À1
and K ¼ 10
À6.13
.
Graphical representation is best approached by dividing the pH range
into two regions, pHopK and pH4pK. The slope of the lines in each
of these two regions can be determined by differentiating (3.45) and
(3.46) with respect to pH.
For pHopK, (Kþ{H
1
})-{H
1
} and
d log {2, 4, 6-TCP}/d pH ¼ d log{H
1
}/d pH þ d log C/d pH
À d log{H
1
}/d pH ¼ 0
pH
0 2 4 6 8 10 12 14
α
0.0
0.2
0.4
0.6
0.8
1.0
α
0
pH=pK
α
1
Figure 1 The influence of pH on a
0
and a
1
for a monoprotic acid
99 Chemistry of Freshwaters
d log {2, 4, 6-TCP
À
}/d pH ¼ d log K/d pH þ d log C/d pH
À d log{H
1
}/d pH ¼ þ1
For pH4pK, (Kþ{H
1
})-K and
d log {2, 4, 6-TCP}/d pH ¼ d log {H
1
}/d pH þ d log C/d pH
À d log K/d pH ¼ À1
d log {2, 4, 6-TCP
À
}/d pH ¼ d log K/d pH þ d log C/d pH
À d log K/d pH ¼ 0
To construct the straight line sections of the graph, note that
log{2,4,6-TCP} ¼ log C for pHopK and log{2,4,6-TCP
À
} ¼ log C
for pH4pK. Then using the full expressions for log{2,4,6-TCP} and
log{2,4,6-TCP
À
}, calculate several points on lines of slope þ1 and À1
to complete the graph.
pH
0 2 4 6 8 10 12 14
-
l
o
g

{
}
3
4
5
6
7
8
TCP H
+
OH
-
TCP
-
{H
+
} ~ {TCP
-
}
The equilibrium pH for a solution containing the weak acid is
obtained by approximating the charge balance expression by
{H
1
}B{TCP
À
} (because the solution will be acidic and thus {OH
À
}
is very small). Conversely, the equilibrium pH for a solution of the
salt of the weak acid is obtained by approximating the appropriate
charge balance expression by {TCP}B{OH
À
} (because the solution
will be basic and so {H
1
} is very small).
Note also that, as shown in Example 3.4, the equilibrium constant, K,
can be corrected for ionic strength of solution. In general, the
equilibrium pH value decreases with increasing ionic strength.
Carbonate Equilibria. Another example of the importance of acid-base
behaviour, not only in aerated freshwaters but also in seawater (see
100 Chapter 3
Chapter 4), is the dissociation of diprotic acids such as carbonic acid,
H
2
CO
3
. The hydration of dissolved CO
2(aq)
in natural waters gives rise
to carbonic acid. The dissociation of carbonic acid not only influences
the pH of the water but also provides ligands which can complex trace
metals. Example 3.6 illustrates the relationship between log { } and pH
for a closed aqueous system which contains dissolved CO
2
(the presence
of mineral phases has been ignored). By assuming that a system is closed
to the atmosphere, it is possible to treat carbonic acid as a non-volatile
acid and to consider only the hydration reaction which converts CO
2(aq)
to H
2
CO
3
. H
2
CO
3
* is used to represent the sum of the activities of
CO
2(aq)
and H
2
CO
3
, i.e. to take account of the presence of CO
2(aq)
,
which is in equilibrium with H
2
CO
3
. The dissociation of carbonic acid
can then be described by (3.50)–(3.51) and the equilibrium constants, K
1
and K
2
, are defined by (3.52)–(3.53).
H
2
CO
*
3
"HCO
À
3
þ H
1
(3.50)
HCO
À
3
"CO

3
þ H
1
(3.51)
K
1
¼ {HCO
À
3
} {H
1
}/{H
2
CO
*
3
} (3.52)
K
2
¼ {CO

3
} {H
1
}/{HCO
À
3
} (3.53)
The analytical activity of dissolved inorganic carbon species can be
written as the sum of undissociated and dissociated acid species (3.54).
For a closed system, the value of C is constant over the entire pH
range.
C ¼ {H
2
CO
*
3
} þ {HCO
À
3
} þ {CO

3
} (3.54)
Combining (3.52)–(3.54), an expression for each of these (H
2
CO
3
*,
HCO
3
À
, and CO
3

) is obtained.
{H
2
CO
*
3
} ¼ C ({H
1
}
2
/({H
1
}
2
þ K
1
{H
1
} þ K
1
K
2
)) (3.55)
{HCO
À
3
} ¼ C (K
1
{H
1
}/({H
1
}
2
þ K
1
{H
1
} þ K
1
K
2
)) (3.56)
{CO

3
} ¼ C (K
1
K
2
/({H
1
}
2
þ K
1
{H
1
} þ K
1
K
2
)) (3.57)
The dissociation fractions, a
0
, a
1
, and a
2
, are obtained by dividing each
of (3.55)–(3.57) by the analytical activity, C (cf. (3.42)–(3.43)).
a
0
¼ {H
1
}
2
/({H
1
}
2
þ K
1
{H
1
} þ K
1
K
2
) (3.58)
101 Chemistry of Freshwaters
a
1
¼ K
1
{H
1
}/({H
1
}
2
þ K
1
{H
1
} þ K
1
K
2
) (3.59)
a
2
¼ K
1
K
2
/({H
1
}
2
þ K
1
{H
1
} þ K
1
K
2
) (3.60)
where
a
0
þ a
1
þ a
2
¼ 1 (3.61)
Graphical representation of log { } vs. pH can again be used to obtain the
equilibrium pH (Example 3.6).
Example 3.6: Graphical illustration of the relationship between (i)
log{H
2
CO
3
*}, (ii) log{H
2
CO
3
}, (iii) log{HCO
3
À
}, and (iv) log{CO
3

}
and pH for a closed aqueous system. Use C ¼ 2 Â 10
À5
mol L
À1
, K
1
¼
5.1 Â 10
À7
and K
2
¼ 5.1 Â 10
À11
.
The presence of dissolved CO
2
is taken into account by the following
equilibrium:
CO
2ðaqÞ
þ H
2
O ÐH
2
CO
3ðaqÞ
K
hydration
¼ fH
2
CO
3
g=fCO
2
g ¼ 1:54 Â 10
À3
We defined {H
2
CO
3
*} ¼ {CO
2
} þ {H
2
CO
3
} but {H
2
CO
3
*}B{CO
2
}
because the hydration equilibrium lies far to the left. So K
hydration
¼
{H
2
CO
3
}/{H
2
CO
3
*} and {H
2
CO
3
} ¼ {H
2
CO
3
*} Â1.54 Â 10
À3
. In this
way the presence of dissolved CO
2
is taken into account while the true
concentration of carbonic acid can still be determined.
By assuming a closed system, the total analytical activity of carbonic
acid, C, is constant [this is not true for an open system (Example 3.7)].
Thus (3.52)–(3.54) can be combined to give (3.55)–(3.57).
For a diprotic acid such as H
2
CO
3
*, the pH range can be divided into
three regions, pHopK
1
, pK
1
opHopK
2
, and pH4pK
2
, and the proce-
dure outlined in Example 3.5, i.e. obtaining logarithmic expressions for
{H
2
CO
3
*}, {HCO
3
À
}, and {CO
3

} and differentiating each with respect
to pH, can then be utilized to construct the plot of Àlog{ } against pH.
For {H
2
CO
3
*}
pHopK
1
: logfH
2
CO
Ã
3
g ¼ 2 logfH
þ
g þ logC À 2 logfH
þ
g
¼ log C
d logfH
2
CO
Ã
3
g=d pH ¼ 0
102 Chapter 3
pK
1
opHopK
2
: logfH
2
CO
Ã
3
g ¼ logfH
þ
g þ log C À log K
1
d logfH
2
CO
Ã
3
g=d pH ¼ À1
pH4pK
2
: logfH
2
CO
Ã
3
g ¼ 2logfH
þ
g þ log C À log K
1
K
2
d logfH
2
CO
Ã
3
g=dpH ¼ À2
The slopes for the other lines are obtained in the same way. Approx-
imating the charge balance expression (3.62) by {H
1
}B{HCO
3
À
} gives
the equilibriumpH for a closed aqueous systemcontaining carbonic acid.
pH
0 2 4 6 8 10 12 14
-
l
o
g
{
}
4
6
8
10
12
H
2
CO
3
*
H
C
O
3
-
C
O
3
2
-
H
+
O
H
-
H
2
CO
3
{H
+
} ~ {HCO
3
-
}
Alkalinity. An important definition arising from the considerations of
carbonate equilibria is that of alkalinity, which is derived with reference
to the charge balance expression for carbonic acid.
{H
1
} ¼ {HCO
À
3
} þ 2{CO

3
} þ {OH
À
} (3.62)
Alkalinity is described as the acid neutralizing capacity of an aqueous
system or equivalently as the amount of base possessed by the system.
Alkalinity ¼ {HCO
À
3
} þ 2{CO

3
} þ {OH
À
} À {H
1
} (3.63)
Species other than carbonate can contribute to alkalinity and an
alternative definition is
Alkalinity ¼fHCO
À
3
g þ 2fCO

3
g þ fNH
3
g þ fHS
À
g þ 2fS

g
þ fH
3
SiO
À
4
g þ 2fH
2
SiO

4
g þ fOrg
À
g þ fHPO

4
g
þ 2fPO

4
g þ fOH
À
g À fH
þ
g À fH
3
PO
4
g ð3:64Þ
103 Chemistry of Freshwaters
In addition to the charge balance expression for H
2
CO
3
, Equation
(3.64) includes appropriate expressions for NH
4
1
, H
2
S, H
4
SiO
4
, HOrg,
and H
2
PO
4
À
. In each case, the reference point has been selected on the
basis of the pK values for these species. For example, phosphoric acid,
H
3
PO
4
, has pK
1
¼ 2.15 and pK
2
¼ 7.20 and so H
2
PO
4
À
will be the main
‘P’ species in solution at the reference point, i.e. the equilibrium pH of a
solution of carbonic acid and water (pHB5.65). The contribution of ‘P’
species to alkalinity is thus determined by using the charge balance
expression for NaH
2
PO
4
.
Another approach to determine carbonate alkalinity is by using a
charge balance expression for the major conservative ions in aqueous
solution.
Carbonate Alkalinity ¼ fHCO
À
3
g þ 2fCO

3
g
¼
X
ðconservative cationsÞ
À
X
ðconservative anionsÞ
¼fNa
þ
g þ fK
þ
g þ 2fCa

g þ 2fMg

g
À fCl
À
g À 2fSO

4
g À fNO
À
3
g
ð3:65Þ
Alkalinity is an important parameter in assessing the effects of envir-
onmental change on aqueous systems (see Section 3.3.4.1). It is also
important to understand that, by definition, alkalinity (Equation (3.61)) is
independent of addition or removal of CO
2
(or H
2
CO
3
) from the system
(cf. Equation (3.62) – H
2
CO
3
does not appear in the charge balance
expression). This can be very useful in the determination of the concen-
tration of dissolved inorganic carbon species in aqueous systems that are
in equilibrium with an atmosphere containing CO
2(g)
(Example 3.7).
Example 3.7: Graphical illustration of the relationship between (i)
log{H
2
CO
3
*}, (ii) log{H
2
CO
3
}, (iii) log{HCO
3
À
}, and (iv) log{CO
3

}
and pH for an open aqueous system. Use p
CO2
¼ 3.5 Â 10
À4
atm, K
H
¼
3.2 Â 10
À2
, K
1
¼ 5.1 Â 10
À7
and K
2
¼ 5.1 Â 10
À11
.
CO
2(g)
þ H
2
O "H
2
CO
3
* K
H
¼ {H
2
CO
3
*}/p
CO2
¼ 3.2 Â 10
À2
mol L
À1
atm
À1
where K
H
is the Henry’s Law constant for atmosphere-aqueous phase
equilibria involving gases.
104 Chapter 3
Clearly, {H
2
CO
3
*} is now a constant for a fixed partial pressure of
CO
2
and is independent of pH, i.e. {H
2
CO
3
*} ¼ K
H
p
CO2
. This means
that {H
2
CO
3
} is also constant over the entire pH range.
Combining this new expression for {H
2
CO
3
*} with (3.52)–(3.53) gives
expressions for {HCO
3
À
} and {CO
3

}:
{HCO
À
3
} ¼ K
1
K
H
p
CO2
/{H
1
} and {CO

3
} ¼ K
1
K
2
K
H
p
CO2
/{H
1
}
2
The analytical activity, C, is not a constant but can be expressed as
C ¼ K
H
p
CO2
/a
0
which increases with increasing pH according to the function (1 þ K
1
/
{H
1
} þ K
1
K
2
/{H
1
}
2
) as shown by the heavy black line on the
accompanying graph.
Plotting Àlog{ } vs. pH for {HCO
3
À
} and {CO
3

} gives lines of slope
þ1 and þ2, respectively. The charge balance expression, which is the
same as that for the closed system, can again be used to determine the
equilibrium pH.
pH
0 2 4 6 8 10 12 14
-
l
o
g

{

}
0
2
4
6
8
H
2
CO
3
*
H
C
O
3
-
C
O
3
2
-
H
+
O
H
-
H
2
CO
3
{H
+
} ~ {HCO
3
-
}
Finally, it is useful to note that the expressions describing the pH
dependence of carbonate species concentration for both closed (Ex-
ample 3.6) and open systems can also be used in mass balance
expressions for metal complexation.
pH Dependence of Complex Formation. Other equilibria such as metal
complexation reactions can be considered as acid–base reactions and
plots of log { } against pH also provide information about the dominant
species present in solution under different geochemical conditions. Hy-
drolysis of metal cations occurs progressively with increasing pH, e.g.
105 Chemistry of Freshwaters
M
31
(aq)
, M(OH)
21
(aq)
, M(OH)
2
1
(aq)
, M(OH)
3
0
(aq)
, and M(OH)
4
À
(aq)
are
the hydrolysis products for many M
III
cations (see Section 3.2.3.2).
M
31
(aq)
is generally found at low pH and only at extremely high pH is
M(OH)
4
À
formed. The dependence of Cr
III
hydrolysis reactions on pH is
illustrated in Example 3.8.
Example 3.8: Determination of Cr
III
speciation in an aqueous solution at
pH 1, 6, and 11. Use {Cr
III
T
} ¼ 10
À6
mol L
À1
and log*b
1
¼ À4.00,
log*b
2
¼ À9.62, log*b
3
¼ À16.75, and log*b
4
¼ À27.77. Assume that no
Cr(OH)
3
is precipitated, i.e. homogeneous solution, and that inorganic
and organic ligands are absent.
Cr

þ H
2
O Ð CrOH

þ H
þ Ã
b
1
Cr

þ 2H
2
O Ð CrðOHÞ
þ
2
þ 2H
þ Ã
b
2
Cr

þ 3H
2
O Ð CrðOHÞ
0
3
þ 3H
þ Ã
b
3
Cr

þ 4H
2
O Ð CrðOHÞ
À
4
þ 4H
þ Ã
b
4
fCr
III
T
g ¼ fCr

g þ fCrOH

g þ fCrðOHÞ
þ
2
g þ fCrðOHÞ
0
3
g
þ fCrðOHÞ
À
4
g ¼ 10
À6
mol L
À1
¼ fCr

g ð1 þ
Ã
b
1
=fH
þ
g þ
Ã
b
2
=fH
þ
g
2
þ
Ã
b
3
=fH
þ
g
3
þ
Ã
b
4
=fH
þ
g
4
Þ
This equation can be solved for {Cr
31
} at various pH values by using
the equilibrium constants for each of the four equilibria above,
e.g. at pH 2, {Cr
31
} ¼ 9.90 Â 10
À7
mol L
À1
.
The concentrations of all other species can be calculated using {Cr
31
}
at each selected pH value,
e.g. at pH 2, {CrOH
21
} ¼ (*b
1
/{H
1
}) {Cr
31
} ¼ 0.01 Â 9.90 Â 10
À7
¼
9.90 Â 10
À9
mol L
À1
.
Plotting Àlog{ } against pH illustrates that the dominant species of
Cr
III
are Cr
31
, Cr(OH)
2
1
, and Cr(OH)
4
À
at pH 1, 6, and 11,
respectively. Alternatively, the same information may be presented
in a plot of mole fraction, w, against pH. The mole fractions can be
obtained by dividing species activity by the total activity of Cr
III
, e.g.
w
Cr31
¼ {Cr
31
}/{Cr
III
T
}.
106 Chapter 3
pH
0 2 4 6 8 10 12 14
-
l
o
g
(
}
4
6
8
10
12
14
16
pH
0 2 4 6 8 10 12 14
χ
0.0
0.2
0.4
0.6
0.8
1.0
Cr
3+
CrOH
2+
Cr(OH)
2
+
Cr(OH)
3
0
Cr(OH)
4
-
Cr
3+
CrOH
2+
Cr(OH)
2
+
Cr(OH)
3
0
Cr(OH)
4
-
It should be noted that, for higher values of {Cr
III
T
}, equilibria for
polymeric species should be included and that Cr(OH)
3
may pre-
cipitate. In the presence of iron, the mixed precipitate Fe
x
Cr
1Àx
(OH)
3
may be formed.
Example 3.9 shows, however, that, for Al
III
, ligands such as F
À
and
SO
4

may compete successfully with the hydroxyl ion at low pH values
(see Section 3.3.1.2). For aqueous systems in contact with solid phases,
107 Chemistry of Freshwaters
the formation of such complexes increases mineral solubility by several
orders of magnitude over that predicted by the solubility product, K
SP
.
The presence of even trace concentrations of organic ligands can have an
even greater effect over a wide pH range on Al
III
speciation (Example
3.9).
12
More generally, complexation clearly has an important role to
play, not only in reducing metal toxicity (see Section 3.3.1.2) but also in
markedly increasing metal ion mobility.
Example 3.9: Determination of Al
III
speciation at pH 2, 6, and 10 in
an aqueous solution where {Al
III
T
} ¼ 1 Â 10
À7
mol L
À1
. Use log *b
1
¼
À4.95, log *b
2
¼ À10.55, log *b
3
¼ À17.25, log *b
4
¼ À22.85,
log b
1 fluoride
¼ 7.00, log b
2 fluoride
¼ 12.70, log b
1sulfate
¼ À3.50,
log b
2 sulfate
¼ 5.00, and log b
1 org
¼ 5.9. Assume SF
À
¼ 5 Â 10
À8
mol L
À1
, SSO
4

¼ 1 Â 10
À4
mol L
À1
, SOrg ¼ 1 Â 10
À7
mol L
À1
and
that no precipitation of Al(OH)
3
occurs.
Hydrolysis only:
fAl
III
T
g ¼fAl

g þ fAlðOHÞ

g þ fAlðOHÞ
þ
2
g
þ fAlðOHÞ
3
g þ fAlðOHÞ
À
4
g
¼10
À7
mol L
À1
¼fAl

g 1 þ
Ã
b
1
=fH
þ
g þ
Ã
b
2
=fH
þ
g
2

þ
Ã
b
3
=fH
þ
g
3
þ
Ã
b
4
=fH
þ
g
4

Main species: pH 2: Al
31
; pH 6: Al(OH)
21
, Al(OH)
2
1
; pH 10:
Al(OH)
4
À
.
Hydrolysis and one inorganic ligand, F
À
:
fAl
III
T
g ¼fAl

g þ fAlðOHÞ

g þ fAlðOHÞ
þ
2
g þ fAlðOHÞ
3
g
þ fAlðOHÞ
À
4
g þ fAlF

g þ fAlF
þ
2
g ¼ 10
À7
mol L
À1
¼fAl

g ð1 þ
Ã
b
1
=fH
þ
g þ
Ã
b
2
=fH
þ
g
2
þ
Ã
b
3
=fH
þ
g
3
þ
Ã
b
4
=fH
þ
g
4
þ b
1
fluoride
fF
À
g þ b
2 fluoride
fF
À
g
2
Þ
108 Chapter 3
Main species: pH 2: Al
31
, AlF
21
; pH 6: Al(OH)
21
, Al(OH)
2
1
; pH 10:
Al(OH)
4
À
.
Hydrolysis and two inorganic ligands, F
À
and SO
4

:
fAl
III
T
g ¼fAl

g þ fAlðOHÞ

g þ fAlðOHÞ
þ
2
g
þ fAlðOHÞ
3
g þ fAlðOHÞ
À
4
g þ fAlF

g
þ fAlF
þ
2
g þ fAlSO
þ
4
g þ fAlðSO
4
Þ
À
2
g ¼ 10
À7
mol L
À1
¼fAl

g ð1 þ
Ã
b
1
=fH
þ
g þ
Ã
b
2
=fH
þ
g
2
þ
Ã
b
3
=fH
þ
g
3
þ
Ã
b
4
=fH
þ
g
4
þ b
1 fluoride
fF
À
g þ b
2 fluoride
fF
À
g
2
þ b
1 sulfate
fSO

4
g þ b
2 sulfate
fSO

4
g
2
Þ
Main species: pH 2: Al
31
, AlF
21
, (AlSO
4
1
); pH 6: Al(OH)
21
,
Al(OH)
2
1
; pH 10: Al(OH)
4
À
.
Hydrolysis, two inorganic ligands, F
À
and SO
4

, and organic ligand,
Org
À
:
fAl
III
T
g ¼fAl

g þ fAlðOHÞ

g þ fAlðOHÞ
þ
2
g
þ fAlðOHÞ
3
g þ fAlðOHÞ
À
4
g þ fAlF

g
þ fAlF
þ
2
g þ fAlSO
þ
4
g þ fAlðSO
4
Þ
À
2
g þ fAlOrg

g
¼ 10
À7
mol L
À1
¼fAl

g ð1 þ
Ã
b
1
=fH
þ
g þ
Ã
b
2
=fH
þ
g
2
þ
Ã
b
3
=fH
þ
g
3
þ
Ã
b
4
=fH
þ
g
4
þ b
1 fluoride
fF
À
g þ b
2 fluoride
fF
À
g
2
þ b
1 sulfate
fSO

4
g
þ b
2 sulfate
fSO

4
g
2
þ b
1 org
fOrg
À

Main species: pH 2: Al
31
, AlF
21
, (AlSO
4
1
); pH 6: AlOrg
21
,
Al(OH)
2
1
; pH 10: Al(OH)
4
À
.
109 Chemistry of Freshwaters
pH
0 2 4 6 8 10 12 14
0.0
0.2
0.4
0.6
0.8
1.0
pH
0 2 4 6 8 10 12 14
pH
0 2 4 6 8 10 12 14
0.0
0.2
0.4
0.6
0.8
1.0
pH
0 2 4 6 8 10 12 14
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Al
3+
AlOH
2+
Al(OH)
2
+
Al(OH)
3
0
Al(OH)
4
-
Al
3+
AlOH
2+
Al(OH)
2
+
Al(OH)
3
0
Al(OH)
4
-
AlF
2+
AlF
2
+
Al
3+
AlOH
2+
Al(OH)
2
+
Al(OH)
3
0
Al(OH)
4
-
AlF
2+
AlF
2
+
AlSO
4
+
Al
3+
AlOH
2+
, Al (OH)
2
+
,
Al(OH)
3
0
Al(OH)
4
-
AlF
2+
AlF
2
+
AlSO
4
+
AlOrg
2+
hydrolysis only
hydrolysis + fluoride + sulfate
hydrolysis + fluoride hydrolysis + fluoride + sulfate+ organic ligand
Influence of Ionic Strength. It should be noted that corrections to take
account of ionic strength as discussed in Section 3.2.1.2 apply not only
to the acid–base equilibrium constants but also to the stability constants
for complex formation.
3.2.4.2 pe as a Master Variable. Chemical speciation is also influ-
enced by the redox conditions prevailing in natural waters. Although
redox reactions are often slow, and therefore species are present at
activities far from equilibrium, they are commonly represented by
thermodynamic equilibrium expressions, which can provide the bound-
ary conditions towards which a system is proceeding.
pe, a parameter describing redox intensity, gives the hypothetical electron
activity at equilibrium. It measures the relative tendency of a solution to
accept or donate electrons with a high pe being indicative of a tendency for
oxidation, i.e. accepting electrons, while a low pe is indicative of a tendency
for reduction, i.e. donating electrons. It is defined as
pe ¼ Àlog{e
À
} (3.66)
The pe scale is thus analogous to the pH scale (pH ¼ Àlog{H
1
}), since a
low value for pe is obtained where the hypothetical {e
À
} is large (pH is
low where {H
1
} is large) and conversely a high value of pe is obtained
110 Chapter 3
where {e
À
} is small (pH is high where {H
1
} is small). pe is related to the
electrode potential, E
H
, by the expression
pe ¼ 16.9 E
H
(V) (3.67)
This relationship can be derived from the Nernst Equation
E
H
¼ E
0
H
þ (2.303 RT n/F) log(P (oxidized species)/
P (reduced species)) (3.68)
where R is the universal gas constant, T the absolute temperature, F the
Faraday constant, and n the number of electrons.
Starting with the equilibrium expression
aA þ bB þ ne
À
"cC þ dD (3.69)
we can write
K ¼ {C}
c
{D}
d
/{A}
a
{B}
b
{e
À
}
n
(3.70)
Logarithmic expressions are then
log K ¼ log ðPðreduced speciesÞ=PðoxidizedspeciesÞÞ À n logfe
À
g
pe ¼ ð1=nÞ log K þ ð1=nÞ log ðPðoxidizedspeciesÞ=Pðreduced speciesÞÞ
Multiply by 2.303 RT/F to give
ð2:303RT=FÞ pe ¼ ð2:303RTn=FÞ log K
þ ð2:303RT n=FÞ log ðPðoxidizedspeciesÞ=Pðreduced speciesÞÞ
Now use the standard Gibbs free energy, DG
0
¼ À2.303 RT logK
¼ –nFE
0
H
to give
ð2:303RT=FÞ pe ¼ E
0
H
þ ð2:303RTn=FÞ logðPðoxidizedspeciesÞ=Pðreduced speciesÞÞ
ð3:71Þ
The right hand side of Equation (3.71) is the same as that of the Nernst
Equation (3.68) and so the left hand side of Equation (3.71) must be
equal to the left hand side of the Nernst Equation (3.68), thus leading to
Equation (3.67). An additional definition is
pe
0
¼ (1/n) log K (3.72)
and so
pe
0
¼ (2.303 RT/F) E
0
H
¼ 16.9 E
0
H
(3.73)
111 Chemistry of Freshwaters
The usefulness of Equation (3.72) will be demonstrated further in
Example 3.10.
Although the electron activity is a hypothetical phenomenon, pe is a
useful parameter to describe the redox intensity of natural systems and
hence the species distribution under prevailing redox conditions (Ex-
ample 3.10).
Example 3.10: Calculate the pe values for the following solutions (298
K, I ¼ 0) (i) a solution at pH 2 containing {Fe
31
} ¼ 10
À4.5
mol L
À1
and
{Fe
21
} ¼ 10
À2.7
mol L
À1
where log K ¼ 13; (ii) a neutral solution
containing {Mn
21
} ¼ 10
À6
mol L
À1
in equilibrium with the solid phase,
Mn
IV
O
2
and log K ¼ 40.84.
(i) At pH 2, the hydrated metal ion has not undergone hydrolysis
to any significant extent:
Fe

þ e
À
Ð Fe

K ¼ fFe

g=fFe

gfe
À
g
pe ¼ log K þ logðfFe

g=fFe


¼13 þ log ð10
À4:5
=10
À2:7
Þ
¼13 À 1:8 ¼ 11:2
(ii)
MnO
2
þ 4H
þ
þ 2e
À
Ð Mn

þ 2H
2
O
K ¼fMn

g=fH
þ
g
4
fe
À
g
2
pe ¼0:5 log K þ 0:5 log ðfH
þ
g
4
=fMn


¼20:42 þ 0:5 log ð10
À28
=10
À6
Þ
¼20:42 À 11 ¼ 9:42
For a fixed pH value (e.g. pH ¼ 2), the species distribution (e.g. where
{Fe
T
} ¼ 1 Â 10
À3
mol L
À1
) at different pe values can be illustrated by
plotting log{ } against pe. This is analogous to the treatment of pH as
a master variable. The pe range is split into two parts, peope
0
and
pe4pe
0
. Using pe
0
¼ (1/n) log K, this becomes {e
À
}4K
À1
and
{e
À
}oK
À1
(because n ¼ 1 in this Example). Thereafter, construction
of the graph is achieved by the same method used in Example 3.5.
112 Chapter 3
-5 0 5 10 15 20
-
l
o
g
{
}
0
5
10
15
{Fe
2+
} {Fe
3+
}
pε = 1/n log K

Redox intensity or electron activity in natural waters is usually deter-
mined by the balance between those processes which introduce oxygen
(e.g. dissolution of atmospheric oxygen, photosynthesis) and those which
remove oxygen (e.g. microbial decomposition of organic matter). Often
these processes are controlled by the availability of inorganic nutrients
such as phosphate and nitrate, e.g. as utilized in the formation of organic
matter during photosynthesis (see Section 3.3.4).
106CO
2
þ 16NO
À
3
þ HPO

4
þ 122H
2
O þ 18H
1
"C
106
H
263
O
110
N
16
P
1
þ 138O
2
(3.74)
The decay of organic matter produced in this manner leads to the
subsequent consumption of oxygen, e.g. by respiration.
C
106
H
263
O
110
N
16
P
1
þ 138O
2
"106CO
2
þ 16NO
À
3
þ HPO

4
þ 122H
2
O þ 18H
1
(3.75)
The decay of organic matter requires the presence of a terminal electron
acceptor and in Equation (3.75) molecular oxygen is reduced to water.
Other terminal electron acceptors present in natural waters include
NO
3
À
, Mn
IV
, Fe
III
, SO
4

, and CO
2
. Once all molecular oxygen has
been consumed, organic matter is decomposed via reactions involving
other terminal electron acceptors in a series determined by the pe
intensity as shown in Table 3.
The sequence of redox reactions involving organic matter, all of which
are microbially mediated, can be thought of as progressing through
113 Chemistry of Freshwaters
decreasing levels of pe and so, for example, NO
3
À
in denitrification
reactions would be utilized as the electron acceptor before Mn
IV
and
SO
4

would be utilized before CO
2
(see Section 3.3.3.2).
Redox processes are important for elements which can exist in more
than one oxidation state in natural waters, e.g. Fe
II
and Fe
III
, Mn
II
, and
Mn
IV
. These are termed redox-sensitive elements. The redox conditions
in natural waters often affect the mobility of these elements since the
inherent solubility of different oxidation states of an element may vary
considerably. For example, Mn
II
is soluble whereas Mn
IV
is highly
insoluble. In oxic systems, Mn
IV
is precipitated in the form of oxyhydr-
oxides. In anoxic systems, Mn
II
predominates and is able to diffuse
along concentration gradients both upwards and downwards in a water
column. This behaviour gives rise to the classic concentration profiles
observed for Mn (and Fe) at oxic-anoxic interfaces as illustrated in
Figure 2.
Other examples of redox-sensitive elements include heavy elements
such as uranium, plutonium, and neptunium, all of which can exist in
multiple oxidation states in natural waters. Redox conditions in natural
waters are also indirectly important for solute species associated with
redox-sensitive elements. For example, dissolution of iron (hydr)oxides
under reducing conditions may lead to the solubilization and hence
mobilization of associated solid phase species, e.g. arsenate, phosphate
(see Sections 3.3.2.1, 3.3.3.2, and 3.3.4.1).
3.2.4.3 pe – pH Relationships. Many redox equilibria also involve the
transfer of protons and so chemical speciation depends on both pe and
pH. Stability relationships involving redox processes can be investigated
via pe–pH diagrams. The region of interest for natural waters displayed
in these diagrams is defined by the stability limits of water, i.e. where the
total partial pressure of oxygen and hydrogen is no greater than 1 atm.
Table 3 Redox processes – terminal electron
acceptors
Terminal electron acceptor pe
O
2
13.75
NO
3
À
(reduction to N
2
)
12.65
Mn
IV
8.9
NO
3
À
(reduction to NH
4
1
) 6.15
Fe
III
À0.8
Reducible organic matter À3.01
SO
4

À3.75
CO
2
À4.13
Source: Adapted with permission from W. Stumm and J.J.
Morgan, Aquatic Chemistry 3rd Edn,
15
r Wiley, 1996.
114 Chapter 3
Upper Limit
O
2(g)
þ 4e
À
þ 4H
1
"2H
2
O
(1)
log K ¼ 83.1 (3.76)
Where p
O2
¼ 1, log p
O2
¼ 0 and
log K ¼ À 4 logfe
À
g À 4 logfH
þ
g
pe ¼20:78 À pH
ð3:77Þ
Lower Limit
2H
1
þ 2e
À
"H
2(g)
log K ¼ 0 (3.78)
or
2H
2
O þ 2e
À
"H
2(g)
þ 2OH
À
log K ¼ À28 (3.79)
Where p
H2
¼ 1, log p
H2
¼ 0 and
log K À 2log K
w
¼ 2log{e
À
} À 2log {H
1
}
or
log K ¼ À2log{e
À
} À 2log {H
1
}
In both cases:
pe ¼ ÀpH (3.80)
For any system, stability relationships between solution phase species
and solid phases can be used to construct peÀpH diagrams representing
Figure 2 Oxic-anoxic boundary in the water or sediment column
15
(Reproduced with permission from ref 15, r John Wiley & Sons Inc. 1996)
115 Chemistry of Freshwaters
species distribution within the upper and lower stability limits of water.
In general, the relationships between pe and pH for redox equilibria
involving proton and electron transfer give lines, e.g. pe ¼ a pH þ b
(where a and b are constants), with slope ¼ a. Redox equilibria
involving only electron transfer give rise to horizontal lines, i.e. pe ¼
b, a ¼ 0. Vertical lines arise from equilibria involving only proton
transfer and pH ¼ c (where c is a constant). The relationships between
pe and pH for As–H
2
O and CrÀH
2
O systems at 298 K and 1 atm total
are shown in Examples 3.11 and 3.12, respectively. The importance of
both As and Cr speciation as represented in these pe–pH diagrams is
discussed further in Sections 3.3.2.1 and 3.3.2.5, respectively.
Example 3.11: Construction of a pe–pH graph for Cr-H
2
O. Assume
that no solid phases are formed.
Acid-base behaviour of Cr
VI
:
HCrO
À
4
"CrO

4
þ H
1
K
1
¼ 10
À6.45
Hydrolysis behaviour of Cr
III
:
Cr

þ H
2
O Ð CrðOHÞ

þ H
þ
K
2
¼ 10
À4:00
CrðOHÞ

þ H
2
O Ð CrðOHÞ
þ
2
þ H
þ
K
3
¼ 10
À5:62
CrðOHÞ
þ
2
þ H
2
O Ð CrðOHÞ
0
3
þ H
þ
K
4
¼ 10
À7:13
CrðOHÞ
0
3
þ H
2
O Ð CrðOHÞ
À
4
þ H
þ
K
5
¼ 10
À11:02
Reduction of Cr
VI
to Cr
III
:
HCrO
À
4
þ 7H
þ
þ 3e
À
Ð Cr

þ 4H
2
O K
6
¼ 10
À70:55
HCrO
À
4
þ 6H
þ
þ 3e
À
Ð CrðOHÞ

þ 3H
2
O K
7
¼ 10
À66:55
HCrO
À
4
þ 5H
þ
þ 3e
À
Ð CrðOHÞ
þ
2
þ 2H
2
O K
8
¼ 10
À60:93
CrO

4
þ 6H
þ
þ 3e
À
Ð CrðOHÞ
þ
2
þ 2H
2
O K
9
¼ 10
À67:38
CrO

4
þ 5H
þ
þ 3e
À
Ð CrðOHÞ
0
3
þ H
2
O K
10
¼ 10
À60:25
CrO

4
þ 4H
þ
þ 3e
À
Ð CrðOHÞ
À
4
K
11
¼ 10
À49:23
Construction of vertical lines:
e.g. K
1
¼ {H
1
}{CrO

4
}/{HCrO
À
4
}
On the line, the concentrations of the Cr
VI
species are equal,
so pH ¼ pK
1
¼ 6.45.
Construction of sloped lines:
e.g. K
8
¼ {Cr(OH)
þ
2
}/{HCrO
À
4
}{H
1
}
5
{e
À
}
3
On the line, the concentrations of the Cr
III
and Cr
VI
species are equal,
so pe ¼ Àlog K
8
/3 – 5/3 pH ¼ 20.31–1.6 pH.
Crossing points:
For the lines defined by K
1
and K
8
, substitute pH ¼ 6.45 in pe ¼
20.31–1.6 pH, so pe ¼ 9.99.
116 Chapter 3
pH
0 2 4 6 8 10 12 14
p
ε
-10
0
10
20
30
Cr
3+
C
r
O
H
2
+
C
r
(
O
H
)
2
+
Cr(OH)
3
0
Cr(OH)
4
-
H
C
r
O
4
-
CrO
4
2-
O
2
/H
2
O
H
2
O/H
2
Example 3.12: Construction of a pe–pH diagram for As–H
2
O. Assume
that no solid phases are formed.
Acid-base behaviour of As
V
:
H
3
AsO
4
Ð H
2
AsO
À
4
þ H
þ
K
1
¼ 10
À2:24
H
2
AsO
À
4
Ð HAsO

4
þ H
þ
K
2
¼ 10
À6:76
HAsO

4
Ð AsO

4
þ H
þ
K
3
¼ 10
À11:60
Acid-base behaviour of As
III
:
H
3
AsO
3
Ð H
2
AsO
À
3
þ H
þ
K
4
¼ 10
À9:23
H
2
AsO
À
3
Ð HAsO

3
þ H
þ
K
5
¼ 10
À12:10
Reduction of As
V
to As
III
:
H
3
AsO
4
þ 2H
þ
þ 2e
À
Ð H
3
AsO
3
þ H
2
O K
6
¼ 10
19:46
H
2
AsO
À
4
þ 3H
þ
þ 2e
À
Ð H
3
AsO
3
þ H
2
O K
7
¼ 10
21:70
HAsO

4
þ 4H
þ
þ 2e
À
Ð H
3
AsO
3
þ H
2
O K
8
¼ 10
28:46
HAsO

4
þ 3H
þ
þ 2e
À
Ð H
2
AsO
À
3
þ H
2
O K
9
¼ 10
19:23
AsO

4
þ 4H
þ
þ 2e
À
Ð H
2
AsO
À
3
þ H
2
O K
10
¼ 10
30:83
AsO

4
þ 3H
þ
þ 2e
À
Ð HAsO

3
þ H
2
O K
11
¼ 10
18:73
Construction of vertical lines:
e.g. K
1
¼ {H
1
}{H
2
AsO
À
4
}/{H
3
AsO
4
}
On the line, the concentrations of the As
V
species are equal,
so pH ¼ pK
1
¼ 2.24.
Construction of sloped lines:
e.g. K
6
¼ {H
3
AsO
3
}/{H
3
AsO
4
}{H
1
}
2
{e
À
}
2
117 Chemistry of Freshwaters
On the line, the concentrations of the As
III
and As
V
species are equal.
so pe ¼ log K/2 – pH ¼ 9.73–pH.
Crossing points:
For the lines defined by K
1
and K
6
, substitute pH ¼ 2.24 in pe ¼ 9.73–
pH, so pe ¼ 7.49.
pH
0 2 4 6 8 10 12
−10
0
10
20
H
3
AsO
4
H
2
AsO
4

HAsO
4
2−
HAsO
3
2−
H
3
AsO
3
H
2
AsO
3

O
2
/H
2
O
H
2
O/H
2
p
ε
A
s
O
4
3

In Examples 3.11 and 3.12 it has been assumed that no solid phases
are formed. At higher solution concentrations, however, the formation
of solid phases such as insoluble hydroxides, carbonates and sulfides
must be considered. The stability of these phases is often pe and/or pH
dependent. Redox equilibria involving both aqueous and solid phase ‘S’
species are shown in Example 3.13.
Example 3.13: Construction of a pe–pH diagram for SO
4
–S
(s)
–H
2
S
system. Use S
T
¼ 10
À2
mol L
À1
.
Acid-base behaviour of S
VI
:
HSO
À
4
"SO

4
þ H
1
K
1
¼ 10
À2.0
Acid-base behaviour of S
ÀII
:
H
2
S
(aq)
"HS
À
þ H
1
K
2
¼ 10
À7.0
Reduction of S
VI
to S
0
:
HSO
À
4
þ 7H
1
þ 6e
À
"S
(s)
þ 4H
2
O K
3
¼ 10
À34.2
118 Chapter 3
SO

4
þ 8H
1
þ 6e
À
"S
(s)
þ 4H
2
O K
4
¼ 10
À36.2
Reduction of S
VI
to S
ÀII
:
SO

4
þ 9H
1
þ 8e
À
"HS
À
þ 4H
2
O K
5
¼ 10
À34.0
Reduction of S
0
to S
ÀII
:
S
(s)
þ 2H
1
þ 2e
À
"H
2
S
(aq)
K
6
¼ 10
4.8
Construction of sloped lines involving a solid phase:
pe ¼ Àlog K
6
/2 – log{H
2
S
(aq)
}/2 – pH
On the line, assume that S
T
¼ log{H
2
S
(aq)
} ¼ 10
À2
mol L
À1
so
pe ¼ 3.4–pH.
pH
0 2 4 6 8 10 12
p
ε
-10
0
10
20
HSO
4
-
SO
4
2-
S
(s)
H
2
S
HS
-
The information contained in this pe–pH diagram is particularly
useful in the determination of stability zones for solid phase metal
sulfides (Example 3.14). For example, it is the reduction of sulfate to
sulfide which determines the stability field of pyrite (FeS
2
).
Example 3.14: Construction of a pe–pH diagram for the Fe–O
2
–‘S’–
CO
2
–H
2
O open system where {Fe
T
} is 1 Â 10
À6
mol L
À1
, {S
(aq) T
} ¼ 1Â
10
À2
mol L
À1
and p
CO2
¼ 10
À3
atm.
Reduction of Fe
III
to Fe
II
:
Fe
31
þ e
À
"Fe
21
K
1
¼ 10
À13.0
Fe(OH)
21
þ e
À
þ H
1
"Fe
21
þ H
2
O K
2
¼ 10
15.2
119 Chemistry of Freshwaters
Fe(OH)
þ
2
þ e
À
þ 2H
1
"Fe
21
þ 2H
2
O K
3
¼ 10
18.7
Fe(OH)
3(s)
þ e
À
þ 3H
1
"Fe
21
þ 3H
2
O K
4
¼ 10
17.9
Fe(OH)
3(s)
þ e
À
þ H
1
"Fe(OH)
2(s)
þ H
2
O K
5
¼ 10
5.5
Fe(OH)
À
4
þ e
À
þ 2H
1
"Fe(OH)
2(s)
þ 2H
2
O K
6
¼ 10
22.2
Reduction of Fe
II
to Fe
0
:
Fe
21
þ 2e
À
"Fe
(s)
K
7
¼ 10
À13.8
Fe(OH)
2(s)
þ 2e
À
þ 2H
1
"Fe
(s)
þ 2H
2
O K
8
¼ 10
1.4
Hydrolysis of Fe
III
:
Fe
31
þ H
2
O "Fe(OH)
21
þ H
1
K
9
¼ 10
À2.2
Fe(OH)
21
þ H
2
O "Fe(OH)
þ
2
þ H
1
K
10
¼ 10
À3.5
Fe(OH)
þ
2
þ H
2
O "Fe(OH)
3(s)
þ H
1
K
11
¼ 10
0.8
Fe(OH)
3(s)
þ H
2
O "Fe(OH)
À
4
þ H
1
K
12
¼ 10
À16.7
Hydrolysis of Fe
II
:
Fe
21
þ 2H
2
O"Fe(OH)
2(s)
þ 2H
1
K
13
¼ 10
À12.4
Carbonate complexation of Fe
II
and additional reduction reactions:
FeCO
3(s)
þ H
1
"Fe
21
þ HCO
À
3
K
14
¼ 10
5.8
Fe(OH)
3(s)
þ HCO
À
3
þ 2H
1
þ e
À
"FeCO
3(s)
þ 3H
2
O K
15
¼ 10
12.1
Fe(OH)
À
4
þ HCO
À
3
þ 3H
1
þ e
À
"FeCO
3(s)
þ 4H
2
O K
16
¼ 10
32.4
In the stability field of sulfate:
SO

4
þ Fe
21
þ 16H
1
þ 14e
À
"FeS
2(s)
þ 8H
2
O K
17
¼ 10
86.8
FeCO
3(s)
þ 2SO

4
þ 14e
À
þ 18H
1
"FeS
2(s)
þ H
2
CO
3
þ 8H
2
O
K
18
¼ 10
85.4
At lower pe values (in the H
2
S and HS
À
stability fields):
FeS
2(s)
þ 4H
1
þ 2e
À
"Fe
21
þ 2H
2
S
(aq)
K
19
¼ 10
À5.0
FeS
2(s)
þ H
1
þ 2e
À
"FeS
(s)
þ HS
À
K
20
¼ 10
À14.6
120 Chapter 3
pH
2 4 6 8 10 12 14
p
ε
-15
-10
-5
0
5
10
15
20
H
2
O/O
2
Fe(OH)
3 ferrihydrite
Fe(OH)
4
-
Fe
2+
FeS
2 pyrite
H
2
/H
2
O
Fe(OH)
2
+
Fe(OH)
2+
Fe
3+
Fe
2+
+ H
2
S
FeS
F
e
C
O
3 siderite
It should be remembered that these diagrams are based on equilibrium
conditions and that redox reactions in natural waters may be far from
equilibrium. Additional assumptions are often made, e.g. the activities of
the main components are fixed and that those of all minor species are
known, the activity of all solid phases is unity, and only a few reactive
components need to be considered.
34
As a consequence, straight line
boundaries between species are generated. Importantly, adsorption, ion
exchange, and metal-organic interactions are often omitted, limiting the
usefulness of classical pe–pH diagrams (e.g. Examples 3.11–3.14).
34
Gen-
eration of more environmentally representative diagrams requires the use
of geochemical computer models (see Section 3.2.5). For example, Kinni-
burgh and Cooper
34
demonstrate how PHREEQC
35
and ORCHESTRA
36
can be used to obtain predominance diagrams (including pe–pH diagrams)
for a wide range of metals, metalloids, and anionic species.
3.2.5 Modelling Aquatic Systems
This chapter has discussed the fundamental importance of the master
variables pe and pH in determining species distribution under the
conditions prevailing in natural systems (pe À10 to þ 17 and pH 4 to
10). The equilibria contained in Sections 3.2.2–3.2.4 also provide the
basis for many of the currently available geochemical computer models
(e.g. WATEQ4F,
30
PHREEQC,
35
and MINTEQA2
22
), which are being
121 Chemistry of Freshwaters
used to predict the geochemical behaviour of metal ions, organic
pollutants, etc. As discussed in Section 3.2.1.2, certain equations, e.g.
Davies equation for activity coefficient calculation, are contained in the
source code of these models. In contrast, a recently developed model,
ORCHESTRA (Objects Representing CHEmical Speciation and
TRAnsport), enables the user to define equations in text format, which
can then be read by the ORCHESTRA calculation kernel.
36
The object-
oriented structure of this model also allows the user to choose appro-
priate chemical models, e.g. for activity coefficient calculation (see
Section 3.2.1.2), adsorption at organic surfaces (MODEL V,
37
NICA
38
),
and adsorption at oxide surfaces (CD-MUSIC
39
).
Overall, geochemical computer models can be extremely useful in the
description of chemical equilibria occurring in the aquatic environment.
In some cases, predictions about reaction kinetics and transport of
species can also be made. The application of geochemical models is not
limited to natural aquatic systems but has been usefully extended to
predict the effectiveness of certain remediation strategies in the treat-
ment of waters emanating from contaminated sites.
40
3.3 CASE STUDIES
3.3.1 Acidification
3.3.1.1 Diatom Records. The onset and flourishing of the Industrial
Revolution, with its dependence for energy upon the combustion of
fossils fuels, especially coal, released huge quantities of sulfur dioxide
and nitrogen oxides to the atmosphere, which ultimately were returned
to the land surface in the form of acid precipitation (H
2
SO
4
, HNO
3
).
The effect of this upon freshwater lakes, especially in poorly buffered
catchment areas (e.g. low-carbonate soils, granitic bedrock) was a
significant decrease in pH and a concomitant decline in biological
productivity, often leading to clear acid waters devoid of fish. That
the acidification of freshwater lakes is a comparatively recent (post-
1850) phenomenon linked to acid deposition has been demonstrated by
the diatom record in the sediments at the bottom of acidified lakes.
41
Diatoms are algae with silicified cell walls. Depending upon the acidity
of the water, some species flourish more than others. Upon deposition,
these siliceous remains are preserved in the sediment column. The
dramatic change in pH after 1850 inferred from the diatom record in
dated sediments from the Round Loch of Glenhead in the Galloway
region of south-west Scotland rules out long-term acidification processes
as the cause.
42
122 Chapter 3
3.3.1.2 Aluminium. The effect of such acidification upon the mobili-
zation, behaviour, and subsequent biological impact of aluminium in
freshwaters has been spectacular. Constituting 8.13% of the Earth’s
crust, aluminium is the third most abundant element and is largely
associated with crystalline aluminosilicate minerals of low solubility. In
the absence of strong acid inputs, processes of soil development nor-
mally lead to only a small fraction of aluminium becoming available to
participate in biogeochemical reactions. Thus, in the Northern Tempe-
rate Region, mobilization of aluminium from upper to lower mineral
horizons by organic acids (or H
2
CO
3
) leached from foliage or forest
floors often leads to the formation of Al(OH)
3
in a process known as
podzolization. Under elevated partial pressures of CO
2
, however, dis-
sociation of H
2
CO
3
produces H
1
, which may solubilize aluminium,
while HCO
3
À
serves as a counterion for transport of cationic Al
III
(aq)
through soil. Upon discharge to a surface water, CO
2
degasses, resulting
in aluminium hydrolysis and precipitation as Al(OH)
3
. Thus, in most
natural waters, concentrations of dissolved aluminium are generally low
due to the relatively low solubility of natural aluminium minerals under
circumneutral pH values. In the case of strong acid (H
2
SO
4
, HNO
3
)
inputs, however, especially to sensitive regions with small pools of basic
cations (Ca
21
, Mg
21
, Na
1
, K
1
) and an inability to retain inputs of
strong acid anions (SO
4

, NO
3
À
, Cl
À
), acidic cations (H
1
, Al
III
) are
transported along with acid anions from soil to surface water.
43
The speciation of dissolved aluminium in surface waters is highly
pH-dependent (see Section 3.2.3.2), with, in a simple system (considering
only monomeric aluminium species) in equilibrium with solid phase
Al(OH)
3
, the aquated ion Al
31
(aq)
predominating at pHo3, progressive
hydrolysis to Al(OH)
21
and Al(OH)
þ
2
in the pH range 4.5–6.5, followed
by Al(OH)
3
0
from pH 6.5 to 7, and then Al(OH)
4
À
predominating as
the pH increases beyond 7. From pH 4.5–7.5, the solubility of alumi-
nium is low and in this range it is often precipitated as Al(OH)
3
. Below
pH 4.5 and above pH 7.5 the concentration of aluminium in solution
increases rapidly. In a part experimental fractionation, part speciation
modelling study of aluminium in acidified Adirondack surface waters in
the north-eastern USA, Driscoll and Schecher
43
found that, in the
absence of organic ligands, Al
31
(aq)
was significant at pHo5, and that
the inorganic monomeric complexes of aluminium predominated at
pH45. In particular, Al–F complexes were the dominant form at pH
5–6 whereas, at pH46, Al–OH species became the major form. In the
presence of organic ligands, however, they found that, over a broad pH
range of 4.3–7.0, alumino-organic complexes were a major component
of the monomeric aluminium. It is the chemically labile inorganic
123 Chemistry of Freshwaters
monomeric aluminium that has been identified as the toxic agent for fish
which, in acidified lakes and streams at aluminium concentrations of
100–200 mg L
À1
, are unable to maintain their osmoregulatory balance
and are susceptible to respiratory problems from coagulation of mucus
and Al(OH)
3
on their gills at their physiological pH of 7.2.
44
In response to a decline in acid deposition as a result of improved
atmospheric emission controls, there was a significant decline from the
early 1980s to the late 1990s in the concentrations of both inorganic and
organic monomeric aluminium in soil solutions draining from mineral
soils and in stream water in New Hampshire, USA (Figure 3).
45
These
decreases in aluminium concentration were accompanied by decreases in
SO
4

concentrations, but there was only a modest increase in stream
water acid-neutralizing capacity and no change in pH. The hydroxyla-
tion of aluminium appears to have been critical in buffering stream
waters against such increases. In a survey of Adirondack lakes in the
north-eastern USA, however, Driscoll and co-workers measured a
Figure 3 Long-term declines in sulfate concentrations mitigate the mobilization of
aluminium in soil solutions and stream water in the Hubbard Brook Experi-
mental Forest, New Hampshire, USA.
45
a–c, annual volume-weighted concen-
trations of a, inorganic monomeric aluminium (Al
i
); b, organic monomeric
aluminium (Al
o
); and c, sulfate (SO
4

) in mineral soil solutions at 750 m (K)
and 730 m (J), and in stream water (triangles)
(Reprinted with permission from ref 45, r Macmillan Publishing, 2002)
124 Chapter 3
significant increasing trend in acid-neutralizing capacity of 1.60 meq L
À1
per year from 1992 to 2000 for 60% of the monitored lakes.
46
Further-
more, there was a growing concentration of dissolved organic carbon in
15% of the lakes, helping to shift the aluminium from its toxic inorganic
form towards less toxic organic forms although likely to delay recovery
of acid-neutralizing capacity. Overall, however, by 2000 both USA and
European surface waters appeared to be on the way to long-term
recovery from acidification, with decreases in SO
4

concentrations,
increases in pH and acid-neutralizing capacity, and decreases in con-
centrations of labile toxic forms of aluminium.
47–49
With respect to human exposure to aluminium in drinking water, it
must be remembered that aluminium has often been deliberately added,
in the form of Al
2
(SO
4
)
3
, to water supplies at treatment works to remove
coloration by organic compounds in reservoirs in upland catchments.
This it achieves by hydrolyzing to a gelatinous, high surface area,
precipitate of Al(OH)
3
, which helps to remove the coloured organic
colloids. It has been suggested, partially because of observed water
aluminium-related dialysis dementia in some chronic renal patients on
artificial kidney dialysis machines in the 1960s and 1970s, that exposure
to low concentrations of aluminium in drinking water, for which there is
a current EC Maximum Admissible Concentration of 200 mg L
À1
, might
be implicated in Alzheimer’s Disease.
50
There is still no proof of this at
present,
51
although it is known that the incidence of senile dementia on
the remote Pacific island of Guam, where bauxite is mined and the local
water is elevated in aluminium, is a hundred-fold greater than in the
USA. Ten years after an accident at Camelford in south-west England in
1988, when 20 tonnes of Al
2
(SO
4
)
3
were emptied directly into the main
water supply, there did appear to be a lasting effect on the cerebral
function of those who had been exposed to greatly enhanced aluminium
concentrations in the tap water.
52
It has been mooted that, for humans,
a high intake of silicic acid (H
4
SiO
4
) could reduce the bioavailability of
aluminium by two orders of magnitude for, at slightly alkaline intestinal
pH, hydroxyaluminosilicates are stable and unavailable for absorp-
tion.
53
This would mimic the situation in nature, where, in the absence
of a strong acid input, the bioavailability of aluminium is kept low by
the formation of hydroxyaluminosilicate species. The latter has been
described as a ‘geochemical brake on an aluminium juggernaut which
would otherwise career into the biotic cycle’.
54
More generally, in
addition to aluminium, the role of other metals, including zinc, copper,
iron, and manganese, in neurodegenerative disease is now under scru-
tiny, there being suggestions of adverse effects upon protein folding and
subsequent oxidative stress.
55
125 Chemistry of Freshwaters
3.3.1.3 Acid Mine Drainage and Ochreous Deposits. One of the major
pollution problems affecting freshwaters is that of acid waters dis-
charged from coal and metal mines.
56
In an active underground coal
mine, pumping lowers the water table. The deeper strata thus become
exposed to air with the result that pyrite (FeS
2
) present is subject to
oxidation, generating acid conditions.
2FeS
2(s)
þ 2H
2
O þ 7O
2(g)
"2FeSO
4(s)
þ 2H
2
SO
4(1)
(3.81)
When mining and pumping cease, the water table returns to its natural
level. While the flooding of the mine stops the direct oxidation of pyrite,
it does bring the sulfuric acid and iron sulfates into solution. Some of the
ferrous ion (Fe
21
) may be oxidized to the ferric ion (Fe
31
), a slow
process at low pH, but one which can be catalysed by bacteria, and the
ferric ion may react further with pyrite.
57
4Fe
21
þ O
2(g)
þ 4H
1
"4Fe
31
þ 2H
2
O (3.82)
FeS
2(s)
þ 14Fe
31
þ 8H
2
O "15Fe
21
þ 2SO

4
þ 16H
1
(3.83)
Underground in the Richmond Mine at Iron Mountain, California,
extremely acidic mine waters have been encountered, with pH ranging
from 1.5 to À3.6 and total dissolved metal (mainly iron) and sulfate
concentrations as high as 200 g L
À1
and 760 g L
À1
, respectively.
58
These
are the most acidic waters known.
On reaching the surface, the acidic mine drainage water is mixed with
air and oxygenated water, leading to rapid oxidation from the ferrous to
the ferric form and the precipitation of the characteristic unsightly orange
ochreous deposits of iron (hydr)oxides, e.g. ferrihydrite (Fe(OH)
3
),
goethite (FeOOH), observed along many stream and river beds.
4Fe
21
þ O
2(g)
þ 4H
1
"4Fe
31
þ 2H
2
O (3.84)
Fe

þ 3H
2
O Ð FeðOHÞ
3ðsÞ
ferrihydrite
þ3H
þ
ð3:85Þ
Fe

þ 2H
2
O Ð FeOOH
ðsÞ
goethite
þ3H
þ
ð3:86Þ
The overall process may be represented as
2FeS
2(s)
þ 15/2O
2(g)
þ 7H
2
O "2Fe(OH)
3(s)
þ 4H
2
SO
4(1)
(3.87)
Microorganisms (e.g. Thiobacillus thiooxidans, Thiobacillus ferrooxi-
dans, Metallogenium) are involved as catalysts in many of the oxidizing
126 Chapter 3
reactions, which would be extremely slow under the prevailing condi-
tions of low pH (e.g. o4.5).
59
The combination of acid waters and
coatings can have devastating effects upon aquatic biota, with depletion
of free-swimming and bottom-dwelling organisms, the loss of spawning
gravel for fish and direct fish mortalities. Typical approaches to treat-
ment of acid mine drainage have included methods to remove the iron
floc by oxidation and to adjust the pH through the use of limestone filter
beds.
3.3.1.4 Acid Mine Drainage and Release of Heavy Metals. The pro-
duction of sulfuric acid from sulfide oxidation in mines can also lead to
the leaching of metals other than iron, with the result that the emerging
acidic waters may be laden with heavy metals. Thus in the former
metalliferous mining area of south-west England, where there are now
many abandoned mine workings, the closure and flooding of the famous
Wheal Jane tin mine in 1992 led to a highly acidic cocktail of dissolved
metals (Cu, Pb, Cd, Sn, As) entering the Carnon and Fal Rivers at 7–15
million litres per day and spreading throughout the surrounding estu-
aries and coastal waters.
60
In the USA, the EPA has identified over 31,000 hazardous waste sites,
with the largest complex of ‘Superfund’ sites to be remediated in western
Montana, in the Clark Fork River Basin where there have been more
than 125 years of copper and silver mining and smelting activities.
Moore and Luoma
61
have characterized three types of contamination
resulting from large-scale metal extraction: primary, consisting of wastes
produced during mining, milling, and smelting and deposited near their
source of origin; secondary, resulting from transport of contaminants
away from these sites by rivers or through the atmosphere to soils,
groundwaters, rivers, etc.; and tertiary, where contaminants may be
remobilized many kilometres away from their point of origin. More
generally, Furrer and co-workers,
62
in an examination of flocs from
streams polluted from acid mine drainage in California and Germany,
found that when aluminium-rich acid mine drainage mixes with near-
neutral surface waters, fluffy aluminium oxyhydroxide flocs precipitate
and move downstream as suspended solids, transporting adsorbed
pollutants, e.g. heavy metal cations such as Pb
21
, Cu
21
, and Zn
21
.
The flocs appear to be formed from aggregation of the aqueous
polyoxocation, AlO
4
Al
12
(OH)
24
(H
2
O)
12
71
[Al
13
], which is toxic and
possibly responsible for the declining fish populations in rivers polluted
by acid mine drainage.
Some of the largest waste deposits occur in tailing ponds containing
acid mine water. In the Clark Fork River Complex, it is estimated that
127 Chemistry of Freshwaters
ponds contain approximately 9000 t arsenic, 200 t cadmium, 90,000 t
copper, 20,000 t lead, 200 t silver, and 50,000 t zinc. These metals enter
streams and rivers as solutes and particulates and contaminate sedi-
ments in the river and reservoirs far downstream from the primary
sources (Figure 4).
61
Downstream concentrations follow an exponential
decline when viewed over several hundred kilometres. The sediment of
Milltown Reservoir, more than 200 km from the mines and smelters at
Butte and Anaconda, is highly contaminated with various metals and
arsenic. It is believed that oxidation-reduction processes release arsenic
from the reservoir sediments and cause contamination of an aquifer
from which water drawn through wells, now closed, contains arsenic
higher than the EPA drinking water standards.
61
Davis and Atkins,
63
however, have pointed out that, in the bottom sediments of the Clark
Fork River channels, the fraction of fine-grained (o63 mm) clay/silt
material, which contains high metal concentrations and to which benthic
organisms are likely to be directly exposed, is small relative to sands and
gravels. Furthermore, the metals occur predominantly in sulfides fre-
quently armoured with an oxide rim and other sparingly soluble phases.
Figure 4 Types of contamination resulting from large-scale metal extraction
(Reprinted with permission from ref 61, rAmerican Chemical Society, 1990)
128 Chapter 3
When open-pit mining ended in the Clark Fork River Complex in
1982, pumping was discontinued, with the result that water began filling
underground shafts and tunnels and the 390 m deep Berkeley pit.
Contaminated acid water containing individual metal and sulfate con-
centrations thousands of times those in uncontaminated water could
flow into an adjacent alluvial aquifer and eventually over the rim of
the pit. Large-scale hard-rock mining in the western USA, especially
Nevada, has greatly increased in recent years, with the result that deep
‘pit lakes’ are likely to form as open-pit metal mines intersecting
groundwater are depleted and shut down.
64
Pit lakes in high sulfide
rock will tend to have poor quality acidic water, although oxidized rock
that contains significant carbonate will produce better quality, near-
neutral pit lake water. Most of the larger existing pit lakes currently
contain water that does not meet standards for drinking water, agricul-
tural water quality, or aquatic life.
64
Factors such as the oxygen status
of the lake, pH, the hydrogeologic flow system, composition of the
wallrock, evapo-concentration, biological activity, and hydrothermal
inputs are all important to the modelling of future water quality and
impact.
Remediation approaches in circumstances like those described here
are based on a variety of physical, chemical, and biological systems.
These include the construction of ponds where sufficient organic matter
is available to establish anaerobic conditions and immobilize at least
some of the metals (e.g. Cu, Pb, Cd, Zn) as sulfides. Similar passive
treatment of tailings-impacted groundwater has also employed precipi-
tation of metal sulfides as the key clean-up step.
65
Active chemical
treatment with lime, producing sludges, and biosorption by reeds,
wetlands, etc., are other methods which have been tried. Subsequent
to the flooding of the Wheal Jane mine, an active treatment (chemical
neutralization) plant and a passive treatment plant, the latter featuring
three schemes differing only in the pre-treatment method (lime dosing,
anoxic limestone drain, lime-free) used to modify the pH of the influent
mine water, were set up. All three systems at the Wheal Jane Passive
Treatment Plant included (i) constructed aerobic reed beds designed to
remove iron and arsenic, (ii) an anaerobic cell to encourage reduction of
sulfate and facilitate removal of zinc, copper, cadmium, and the
remaining iron as metal sulfides, and (iii) aerobic rock filters designed
to promote the growth of algae and facilitate the precipitation of
manganese.
66
The study showed considerable success in the removal
of key toxic metals and clearly demonstrated the potential for natural
attenuation of acid mine drainage, particularly iron oxidation, by
microbial populations.
129 Chemistry of Freshwaters
3.3.2 Metals and Metalloids in Water
3.3.2.1 Arsenic in Groundwater. In what has been described as the
largest arsenic poisoning epidemic in the world, hundreds of thousands
of people in West Bengal (India) have been seriously affected by arsenic
poisoning resulting from the consumption of water drawn from tube
wells sunk some 20 to 150 m below the ground into aquifers.
67
In West
Bengal, Bangladesh, and other parts of the world (e.g. Chile, Mexico,
Argentina, Ghana, Mongolia, and Taiwan) where inorganic arsenic
concentrations in drinking water are elevated (mg L
À1
vs. WHO
recommended limits of 10 mg L
À1
), exposure has resulted in hyperpig-
mentation, hyperkeratosis, and cancer of the skin and various internal
organs.
68–72
Sulfide minerals are one of the most important natural sources of
arsenic in groundwater. Oxidation of arsenopyrite (FeAsS), in analo-
gous fashion to pyrite (FeS
2
), may release high concentrations of arsenic
into solution.
73,74
4FeAsS
(s)
þ 13O
2(g)
þ 6H
2
O "4Fe
21
þ 4AsO

4
þ 4SO

4
þ 12H
1
(3.88)
In Bengal and Bangladesh, it has been suggested that large-scale with-
drawal of groundwater for irrigation produces seasonal fluctuation of the
water table, which in turn results in intake of oxygen into the pore waters
of sediments that are arsenic-rich in the form of arsenopyrite.
73,74
The
exact speciation of soluble inorganic arsenic, e.g. as the undissociated
forms or different oxyanions of the acids H
3
As
III
O
3
and H
3
As
V
O
4
, will be
dependent upon the prevailing pe and pH. Sorption of arsenic, especially
pentavalent arsenate (e.g. AsO
4

, HAsO
4

, H
2
AsO
4
À
), onto ferric
hydroxide (Fe(OH)
3
) produced under oxidizing conditions may, however,
restrict its mobility and availability, although fertilizer phosphate present
in groundwater could perhaps displace the arsenate. Arsenite, especially
as H
3
As
III
O
3
(pK
1
¼ 9.2), the predominant form under reducing condi-
tions at pHo9.2, is much less strongly sorbed.
As an alternative to the theory of arsenopyrite oxidation, however,
especially where there is an absence of elevated concentrations of sulfate,
it has been proposed that elevated arsenic concentrations in Bengal and
Bangladesh groundwater could result from the release of adsorbed
arsenate during the dissolution of hydrous iron oxides (similar to ferric
hydroxide) under reducing conditions (see Section 3.3.3.2).
73–76
This
phenomenon can be seen in those parts of Asia where sub-strata consist
of recent alluvial sediments, rich in decaying organic matter, that were
deposited and buried during the post-glacial period. Indeed, McArthur
130 Chapter 3
and co-workers
77
believe that the proximity of soluble organic matter to
drive FeOOH reduction is the key and that this can only occur at the
margins of buried peat basins. There is an alternative theory, pro-
pounded by Harvey and co-workers,
78
that the arsenic mobilization is
associated with the inflow of younger carbon, probably untreated hu-
man waste in water that has been drawn into the aquifers of Bangladesh
as a consequence of irrigation pumping.
Although trivalent inorganic arsenic, with its propensity for binding
to the SH group of enzymes, is acknowledged to be more toxic to
humans than pentavalent inorganic arsenic, it must be recognized that
As
V
can be converted to As
III
in the human body as part of the
reduction/biomethylation pathway of excretion
As
V
-As
III
-MMAA -DMAA (3.89)
where MMAA (CH
3
AsO(OH)
2
, monomethylarsonic acid) and DMAA
((CH
3
)
2
AsO(OH), dimethylarsinic acid) are less toxic metabolites, the
latter predominating as the major form of arsenic excreted in urine.
68–72
There is evidence to suggest, however, that trivalent metabolic inter-
mediates of MMAA and DMAA may be highly implicated in the
initiation of cancer.
70–72
Methylation could also occur naturally by
microbial action in freshwaters, although reported occurrences suggest
that the effect is small.
79
3.3.2.2 Lead in Drinking Water. The naturally soft, slightly acidic,
plumbosolvent water of the Loch Katrine water supply for the Glasgow
area was recognized many years ago to release lead from the lead pipes
and tanks in the domestic plumbing of the Victorian and subsequent
(even post-World War II) eras.
80
O
2(g)
þ 4H
1
þ 4e
À
"2H
2
O E
0
H
¼ 1.229 V (3.90)
Pb
21
þ 2e
À
"Pb
(s)
E
0
H
¼ À0.126 V (3.91)
O
2(g)
þ 4H
1
þ 2Pb
(s)
"2Pb
21
þ 2H
2
O E
0
H
¼ 1.355 V (3.92)
Essentially, elemental lead becomes soluble in acidic conditions due
to its oxidation by dioxygen. Furthermore, compounds such as carbo-
nate and hydroxycarbonate compounds of lead, i.e. PbCO
3
and Pb
3
(CO
3
)
2
(OH)
2
, that may coat the pipes, will dissolve under acid condi-
tions.
In view of the concern over detrimental effects of exposure to lead
upon human health, in particular the possible impact upon intelligence
131 Chemistry of Freshwaters
and behaviour of young children, steps were taken in the mid-1970s to
reduce the lead content of tap water in Glasgow and other susceptible
areas, which often exceeded the WHO maximum guideline at the time of
100 mg L
À1
. The method chosen was adjustment of pH to 8–9 by lime
dosing. The effects of liming the Glasgow water supply were quite
dramatic. Whereas pre-1978, when the pH was 6.3, only 50% of random
daytime samples were o100 mg L
À1
in lead, the figure increased to 80%
during 1978–1980, when the adjusted pH was 7.8. After 1980, when the
pH was increased further to 9.0, 95% of samples were o100 mg L
À1
.
80
It
appears that carbonate and hydroxycarbonate lead compounds present
in the coatings on the pipes were stabilized. Significant reductions in
blood lead levels of key exposed groups (e.g. pregnant women) were also
observed.
Since 1989, as regulatory upper limits for lead in drinking water have
fallen, e.g. to 50 mg L
À1
(EC) and now to 10 mg L
À1
(WHO), orthopho-
sphate has been added to the water supply in Glasgow to precipitate
insoluble lead compounds such as Pb
3
(PO
4
)
2
and Pb
5
(PO
4
)
3
OH. This has
resulted in a fall in the proportion of households with water lead 410 mg
L
À1
from 49% in 1981 to 17% in 1993.
81
Despite this improvement, an
estimated 13% of infants were still exposed via bottle feeds to tap water
lead concentrations in excess of 10 mg L
À1
and it seems very unlikely that
further treatment of the water supply will be able to guarantee water lead
concentrations o10 mg L
À1
.
Occasionally, elevated concentrations of lead in tap water arise from
the illegal use of lead solder in capillary joints to join copper pipes.
Cu
21
þ 2e
À
"Cu
(s)
E
0
H
¼ 0.337 V (3.93)
Cu
21
þ Pb
(s)
"Cu
(s)
þ Pb
21
E
0
H
¼ 0.463 V (3.94)
In Washington DC, USA, where the water disinfection programme was
recently modified from chlorine to chloramines, an unexpected appear-
ance of high levels of lead in the tap water has been partly attributed to
similar galvanic corrosion when copper pipes are connected to lead-
containing brass fittings in the presence of chloramines. With the shift to
chloramines, the oxidizing potential of Washington DC’s water was
lowered and not only could the brass become highly anodic and the
copper cathodic, but also the previously deposited PbO
2
scales on the
inside of lead service pipes began to dissolve.
82
3.3.2.3 Cadmium in Irrigation Water. In the 1950s in Japan, many
people, especially menopausal women suffering from malnutrition, low
132 Chapter 3
vitamin D intake, and calcium deficiency, suffered a condition known as
Itai-Itai (Ouch-Ouch) disease, with symptoms ranging from lumbago-
type pains to multiple fractures of softened bones. The cause was
irrigation water from a river (Jintsu) chronically contaminated with
dissolved cadmium from a zinc mining and smelting operation. Con-
taminated rice from the irrigated paddy fields was eaten and the Ca
21
in
bones replaced by Cd
21
, an ion of the same charge and size.
Although this is a particularly extreme example of acute effects
resulting from high exposure to this non-essential element, concern
has been expressed about chronic effects (e.g. kidney damage, hyperten-
sion) from possible enhanced exposure of humans through increased
application of sewage sludge to agricultural land, in view of EC-
enforced cessation of dumping at sea by 1999. Compared with other
heavy metals, cadmium exhibits an especially high mean sludge con-
centration (20 mg kg
À1
) relative to mean soil concentration (0.4 mg
kg
À1
).
83
In acidic soils the concentration of Cd
21
available for uptake by
plants can be substantial,
84
as it adsorbs only weakly onto clays, whereas
at pH 47 it readily precipitates, e.g. as CdCO
3
for which the solubility
product, K
SP
¼ 1.8 Â 10
À14
, is indicative of the advantages of liming.
Similarly, in drinking water, the presence of dissolved carbonate at a
concentration of 5 Â 10
À4
mol L
À1
can reduce the solubility of cadmium
from 637 to 0.11 mg L
À1
, in line with evidence that hard water, with a
high calcium content, can protect against cadmium.
85
3.3.2.4 Selenium in Irrigation Water. In 1983, high rates of embryo-
nic deformity and death, attributed to selenium toxicosis, were found in
wild aquatic birds at the Kesterson National Wildlife Refuge in the San
Joaquin Valley of California.
86
Kesterson Reservoir was a regional
evaporation pond facility where drainage waters, often containing high
level of salts and trace elements (including selenium), from irrigated
farmland had been collected since 1978.
With evapotranspiration, greatly in excess of precipitation, bringing
soluble salts to the surface of farmland in the arid climate of the west-
central San Joaquin Valley, and crop productivity, after irrigation,
threatened by shallow saline groundwater near the root zone, grids of
sub-surface tile drains were constructed to divert the saline waters to a
collective drain (San Luis), which flowed into Kesterson Reservoir. It
was the geologic setting of the San Joaquin Valley as well as the climate,
however, which led not only to the soil salinization but also to the
presence of selenium (in the form of SeO
4

) in Kesterson inflow waters
at concentrations well in excess of the USEPA designation of 1000 mg
L
À1
for selenium as a toxic waste, never mind its 10 mg L
À1
limit for
133 Chemistry of Freshwaters
drinking water and the o2.3 mg L
À1
limit subsequently suggested for the
protection of aquatic life.
To the west of the San Joaquin River (Figure 5), selenium in the soils is
believed to be of natural origin. During the Jurassic and Cretaceous
periods, there was deposition of marine sediments comprising sandstones,
shales, and conglomerates, including seleno-sulfides of iron (FeS
2
þ FeSe
2
).
Subsequent uplifting of these sediments produced the Coast Ranges and
Figure 5 The Kesterson effect: biogeochemical cycling of selenium in the Coast Ranges,
San Joaquin Valley, and Kesterson National Wildlife Refuge of California
(Reproduced with permission from ref 86, r Springer Verlag, 1994)
134 Chapter 3
subjected the sediments to weathering under oxidizing conditions. With
resultant acid neutralized by the carbonate component of the sediments, the
predominant form of selenium produced from oxidation of selenide, Se
ÀII
,
under alkaline conditions, is selenate, Se
VI
O
4

, in preference to selenite,
Se
IV
O
3

, or biselenite, HSe
IV
O
3
À
.
87
Thus the soils on the Coast Ranges,
which are alkaline, contain significant amounts of soluble mineral salts
(e.g. Na
2
SO
4
.10H
2
O, Na
2
Mg(SO
4
)
2
.4H
2
O), including selenates (e.g. Na
2
SeO
4
.10H
2
O, Na
2
Mg(SeO
4
)
2
.4H
2
O).
The chemistry and mobility of selenite and selenate differ greatly in
soils. Selenite is adsorbed by specific adsorption processes (e.g. on clays
and hydrous metal oxides) and to a much greater extent than selenate,
which is adsorbed, like sulfate, by comparatively weak non-specific
processes. Thus, in aerated alkaline soils, such as those of semi-arid
regions like the west-central San Joaquin Valley, mobile Se
VI
O
4

will be
the dominant form and, through runoff, be capable of entering the
groundwaters and sub-surface drainage waters, ultimately being re-
moved to Kesterson Reservoir. There, it is taken up by the biota, with
such devastating effects, and also converted to a range of selenium-
containing species (e.g. Se
IV
O
3

, Se
0
, H
2
Se, Se-rich protein), with much
ultimately being deposited in the sediments. There, over geological time,
natural diagenetic processes would presumably lead again to the for-
mation of reduced seleno-sulfide species.
Considerable effort has been devoted to the clean-up of Kesterson
Reservoir, which was drained in 1987, one year after the input of drainage
water was stopped. Natural processes, stimulated by the addition of
nutrients, of summertime microbial conversion and volatilization to the
atmosphere of methylated forms such as dimethylselenide, (CH
3
)
2
Se, and
downwards leaching of Se
VI
O
4

by percolating water in winter helped to
dissipate 68–88% of total selenium from the topsoil (0–15 cm) over a
period of eight years.
88
Phytoremediation techniques were also tested.
Similarly, pilot bioreactors were set up to convert drainage water SeO
4

into commercially useful selenium-containing products. Although Kes-
terson Reservoir has been closed, selenium loading in the Central Valley
of California, the San Joaquin River, the San Joaquin-Sacramento Delta,
and San Francisco Bay still occurs and an emerging selenium contamina-
tion issue is developing in south-eastern Idaho, USA, in streams draining
areas with phosphate mining activities.
89
3.3.2.5 Chromium in Groundwater. Millions of tonnes of high-pH
chromite ore processing residue (COPR) were deposited (e.g. as landfill
material) in the past in urban areas such as Glasgow, Scotland,
90
and
Hudson County, New Jersey, USA.
91
Even now the high-lime process
135 Chemistry of Freshwaters
responsible for the generation of this waste continues to be used in
countries such as China, Russia, Kazakhstan, India, and Pakistan.
92
In
Glasgow, the chromium content of this residue is high at 3–4% w/w but,
more significantly, elevated concentrations as high as B1% w/w of
highly toxic and carcinogenic hexavalent chromium, which takes the
form of chromate (Cr
VI
O
4

) at the prevailing high pH of 9–12 char-
acteristic of high-lime COPR, have been measured in the solid phase at
the contaminated sites. Furthermore, on sites in the Glasgow area where
COPR from a high-lime chemical works was last deposited in the 1960s,
Cr
VI
is still leaching out in such quantity that receiving groundwaters
and streams in the area are seriously contaminated at concentrations of
up to 100 mg L
À1
, about 2000 times greater than Environmental Quality
Standards (EQSs).
93
There are many problems involved in the in situ application of
remediation-by-reduction methods, e.g. employing Fe, Fe
II
, or organic
compounds, to reduce Cr
VI
held in specific mineral phases within COPR
to the much less harmful trivalent Cr
III
. For example, the use of ferrous
iron, Fe
21
, from ferrous sulfate, rather than reduce the Cr
VI
O
4

held
within the COPR via
2CrO

4
þ 6Fe
21
þ 13H
2
O -Cr
2
O
3(s)
þ 6Fe(OH)
3(s)
þ 8H
1
(3.95)
actually increases the release of CrO
4

because of anion exchange of
SO
4

from the ferrous sulfate for CrO
4

held in the layered double
hydroxide mineral hydrocalumite within the COPR.
94
In principle,
many of the problems involved in the in situ application of methods
designed to reduce Cr
VI
held within COPR to Cr
III
can be avoided if the
emphasis is switched to treatment of the Cr
VI
released to groundwater
and surface water from COPR. Where the objective is to treat ground-
water either in a conventional pump and treat system or as it migrates
through a permeable reactive barrier, there is much less impediment to
chemical methods using Fe
II
or Fe
0
or S

:
95–97
2CrO

4
þ 3H
2
S
(aq)
þ 2H
2
O -2Cr(OH)
3(s)
þ 3S
(s)
þ 4OH
À
(3.96)
More generally for Cr
VI
-contaminated groundwater, which may also
arise from other industrial activities such as tanning and electroplating,
both in situ
98
and pump and treat methods could employ biological as
well as chemical methods for the reduction of Cr
VI
to Cr
III
, for example
in packed bed bioreactors.
99
Another generic method for the reduction of Cr
VI
to Cr
III
is the
addition of organic matter, for example as horse dung or molasses. Such
treatment, however, whether for direct chemical reduction (cf. Equation
136 Chapter 3
(3.111)) or, in conjunction with other nutrients, to stimulate bacterial
reduction of Cr
VI
, could provide a means of retention of Cr
III
in solution
in preference to either precipitation of Cr(OH)
3
or reoxidation to Cr
VI
under the prevailing alkaline conditions of high-lime COPR sites.
Farmer and co-workers
93
found that o3% of dissolved chromium
was present as Cr
VI
in groundwater at one Glasgow borehole site with
a high dissolved organic carbon content of 300 mg L
À1
. Here the
chromium occurred predominantly as Cr
III
in association with organic
material of high molecular weight, with an implied reduction of Cr
VI
by
humic substances, perhaps via carboxylate groups, and the formation of
Cr
III
-humic complexes.
Although the drinking water supply of people in the Glasgow area is
not threatened by the Cr
VI
-contaminated groundwater, there are in-
stances elsewhere of such problems. For example, a massive plume of
Cr
VI
-contaminated groundwater in the Mojave Desert, with concentra-
tions as high as 12 mg L
À1
, was reported to be within 40 m of the
Colorado River, which supplies drinking water to California, USA.
100
This contamination arises from when an electric utility used Cr
VI
to
control corrosion and mould in water-cooling towers and then dumped
untreated wastewater into percolation beds in the 1950s and 1960s.
Current short-term emergency pumping, transport, and offsite treatment
of the contaminated groundwater will have to be replaced by a long-
term solution close to the river, possibly featuring in situ groundwater
treatment or the installation of a permeable reactive barrier in which
iron would reduce Cr
VI
to Cr
III
.
3.3.2.6 Aquatic Contamination by Gold Ore Extractants. The separate
use of mercury and cyanide has led to the contamination of freshwater
systems.
3.3.2.6.1 Mercury in the Amazon Basin. With the price of gold
soaring in the late 1970s and early 1980s, there developed a modern-
day gold rush in South America,
101
which reached its peak during 1990–
1993.
102
In the relatively inaccessible Amazon area in Brazil, there were
up to a million people operating on an informal basis. The technique
which is used to extract the placer gold which has accumulated in many
stream and alluvial deposits is based on amalgamation with mercury.
Typically, high-pressure water hoses are used to dislodge alluvium,
which is then taken into a large sluice by a motor suction pump. The
sluices are lined with sacking into which mercury is added to amalga-
mate the gold particles, which lodge in the sacking. In other versions, no
mercury is used in the sluices. Instead, material is collected from the
137 Chemistry of Freshwaters
sluice lining and crushed in an oil drum, where the mercury is then
introduced, followed by manual panning.
The effects of all this activity can be seen in the increased turbidity,
with clear rivers turning a muddy brown colour, and increased fish
mortality. Furthermore, releases of mercury to the aquatic environment
have resulted in elevated concentrations of mercury in sediments and
fish. Commonly eaten fish species from the Madeira River were found to
contain mean mercury levels of 0.7 mg kg
À1
and up to 3.8 mg kg
À1
in the
Tapajos Valley.
103
Given the bioaccumulation and biomagnification of
mercury in many fish species and the possible microbial methylation of
mercury deposited in sediments to the even more toxic lipid-soluble
methyl mercury, CH
3
Hg
1
, there is a real prospect of enhanced dietary
uptake of the most toxic form of mercury by the local populations. This
would be in addition to exposure from inhalation of mercury vapour
during the handling of mercury and from subsequent post-amalgama-
tion treatment steps, which usually involve refinement of the extracted
gold by heating to drive the more volatile mercury off. It is thought that
there is an annual discharge of about 100 tonnes of mercury into the
Amazon ecosystem and perhaps the same amount released as mercury
vapour. Thus there could be an increased risk of the neurological
damage and foetal deformities commonly associated with mercury
poisoning, as most notably exemplified in the fishing village population
of Minimata, Japan, in the 1950s, when a chemical manufacturing plant
discharged mercury salts and CH
3
Hg
1
into the bay, to be taken up by
fish and shellfish.
3.3.2.6.2 Cyanide. Another method of extracting gold that can lead
to contamination of freshwater is cyanide heap leaching, which is used
to extract tiny amounts of gold from huge volumes of low-grade
deposits of gold-bearing rock. In this case, ore is dug from open-pit
mines, crushed, and spread on asphalt or plastic pads. The heaps are
then sprayed with cyanide, which dissolves the gold.
4Au
(s)
þ 8NaCN þ 2H
2
O þ O
2(g)
-4NaOH þ 4NaAu(CN)
2
(3.97)
The gold-bearing cyanide solutions run off on impermeable asphalt or
plastic to collection vats and are then treated, for example with zinc, to
extract gold.
2NaAu(CN)
2
þ Zn
(s)
-Na
2
Zn(CN)
4
þ 2Au
(s)
(3.98)
One major environmental problem with this technique is that cyanide is
highly toxic. Although attempts are made to loop the cyanide through a
closed system to try to ensure that none is lost, cyanide does commonly
138 Chapter 3
escape to surface waters and groundwater. While cyanide quickly
decomposes in oxygenated, acidic surface water, it can persist at toxic
levels for much longer periods in groundwater and thus pose a longer-
term threat.
3.3.3 Historical Pollution Records and Perturbatory Processes in Lakes
3.3.3.1 Records – Lead in Lake Sediments. Under ideal circumstances,
freshwater lake sediments can preserve the record of temporal variations
in anthropogenic input of contaminants via atmospheric deposition,
catchment runoff, effluent inflow and dumping from industrial, transpor-
tation, mining, agricultural, and waste disposal sources.
104
Prerequisites
are transfer of contaminants associated with settling inorganic particu-
lates and/or biotic detritus from the water column to the sediments, no
disturbance of sediments by physical mixing, slumping or bioturbation
after deposition, no post-depositional degradation or mobility of the
contaminants, and the establishment of a reliable time axis (e.g. via the use
of the naturally-occurring radionuclide
210
Pb, half-life 22.35 years, and
the nuclear fallout radionuclide
137
Cs, half-life 30.2 years).
The derived records of lead deposition to sediments in Loch Ness and
the northern and southern basins of Loch Lomond, Scotland, over the
past few hundred years since the onset of the Industrial Revolution are
shown in Figure 6.
105
The noticeable change in the
206
Pb/
207
Pb ratio of
the lead deposited from the late 1920s onwards is attributed to car-
exhaust emissions of lead of lower
206
Pb/
207
Pb ratio as a result of the use
of lead ores from Broken Hill, Australia, in the manufacture of alkyllead
additives for the UK market. On the basis of the published literature,
there appears to be reasonable confidence that, in the absence of post-
depositional mixing, sediments do, in general, preserve a record of the
deposition of lead to the sediments.
105–107
Many such records in Western
Europe and North America now show concentrations of lead declining
towards the sediment surface as a consequence of the withdrawal of
leaded petrol and also a reduction in other emissions.
105,108
Longer-term
palaeolimnological records, stretching back over several thousand years,
demonstrate the influence of lead mining and smelting in Greek–Roman
times and the later impact of the Mediaeval mining industry.
109
3.3.3.2 Perturbatory Processes in Lake Sediments. The extent to
which conditions for preservation of records are met depends upon
the characteristics of the specific individual systems and contaminants
under study. In reviewing the perturbation of historical pollution
records in aquatic sediments, Farmer
110
has suggested that in the case
139 Chemistry of Freshwaters
of heavy metal behaviour in freshwater lakes there should ideally be
investigation of
different systems of varying status (e.g. oligotrophic, eutrophic,
acid),
Figure 6 Fluxes (J) and associated
206
Pb/
207
Pb ratios (K) of anthropogenic lead
deposited in the sediments of Loch Ness, northern Loch Lomond and southern
Loch Lomond (Scotland), derived from analysis of sections of
210
Pb-dated
sediment cores, vs. calendar date since the 17th century. Dates prior to
approximately 1860 should be considered as extrapolations
(Reprinted with permission from ref 105, r Elsevier, 2002)
140 Chapter 3
seasonal influences,
modes of element introduction and transport,
element associations in the water column,
depositional and redistributional processes and rates (e.g. via
radionuclide and stable isotope studies) in the sediments,
concentration profiles and speciation in the overlying water, solid
sediment, and pore water,
element/solid phase associations (e.g. via sequential chemical
extraction procedures), and
authigenic mineral identification in the sediments.
While opinions may differ as to whether particular sediment columns
have been disturbed by mixing or the extent to which certain elements are
vertically mobile, it is accepted that post-depositional redox-controlled
cycling can affect the vertical profiles of manganese and iron.
111,112
The
driving force is the microbiological decomposition of organic matter
(represented as CH
2
O) through bacterial utilization of O
2
and inorganic
oxidizing agents in thermodynamically favoured sequence.
113
DG
0
(kJ mol
À1
CH
2
O)
CH
2
O þ O
2(g)
"CO
2(g)
þ H
2
O À475 (3.99)
5CH
2
O þ 4NO
À
3
"2N
2(g)
þ 4HCO
À
3
þ CO
2(g)
þ 3H
2
O À448 (3.100)
CH
2
O þ 3CO
2(g)
þ H
2
O þ 2MnO
2(s)
"2Mn
21
þ 4HCO
À
3
À349 (3.101)
CH
2
O þ 7CO
2(g)
þ 4Fe(OH)
3(s)
"4Fe
21
þ 8HCO
À
3
þ 3H
2
O À114 (3.102)
2CH
2
O þ SO

4
"H
2
S
(g)
þ 2HCO
À
3
À77 (3.103)
2CH
2
O "CH
4(g)
þ CO
2(g)
À58 (3.104)
Upon dissolution of oxides and (hydr)oxides of manganese and iron
under reducing conditions at depth, divalent cations of these elements
can diffuse upwards through the pore waters to be oxidized and
precipitated in near-surface oxic layers, leading to the characteristic
near-surface enrichment of manganese and iron in the sediments of
many well oxygenated lakes (see Section 3.2.4.3). Phosphorus and
141 Chemistry of Freshwaters
arsenic are also recycled but in their case it is the negatively charged
anions that are released into solution from an association with solid
phase ferric (hydr)oxides, which dissolve under sufficiently reducing
conditions. Upward diffusion of reduced species leads ultimately to
surface enrichment via co-precipitation or adsorption of phosphate and
arsenate on iron (hydr)oxides in surface layers. As a result, arsenic
concentrations as high as 675 mg kg
À1
can be found near the surface of
Loch Lomond sediments, compared with background values of 15–50
mg kg
À1
at depth.
114
Enrichments of phosphorus and arsenic have
similarly been found in association with authigenic iron oxides in
sedimentary Fe/Mn layers in Lake Baikal where, however, enrichments
of molybdenum were found associated with manganese oxides, perhaps
through mixed oxide formation.
115
For lakes which have undergone significant acidification, it has been
suggested that heavy metals could be released from surface sections by
pH-dependent dissolution, resulting in sub-surface maxima in sedimen-
tary heavy metal concentrations. In two Canadian acid lakes, however,
Carignan and Tessier
116
found that downward diffusive fluxes of
dissolved zinc from overlying waters into anoxic pore waters were
responsible for the pronounced sub-surface sediment maxima in solid
phase zinc, presumably as the insoluble sulfide.
Traditionally, heavy metals such as lead, zinc, copper, and cadmium have
been considered diagenetically (i.e. as a consequence of chemically and
biologically induced changes in prevailing sedimentary conditions, e.g. pe,
anionic composition, etc.) immobile and fixed in the sediment after
deposition, partly as a result of the formation of comparatively insoluble
sulfides under reducing conditions at depth. This may well be an over-
simplified view, as interactions and formation of complexes between metals
and dissolved organic matter (e.g. humic substances) may maintain
dissolved metal concentrations at levels greater than those predicted by
simple solubility product calculations (see Sections 3.2.3.5 and 3.2.4.1).
117
A
combination of geochemical modelling, incorporating interactions of me-
tals with mineral phases and naturally occurring organic matter,
34,118
and
the development of increasingly sophisticated analytical technology, such
as DET (diffusive equilibration in thin films)
119
and DGT (diffusive
gradients in thin films) for the high-resolution determination on a sub-
millimetre scale of metals in sedimentary pore waters,
120
offers considerable
promise for greater understanding of redox-driven cycling of trace elements
in lakes. Not only have fine structure and sharp-featured maxima been
observed for manganese, iron, sulfide, and some trace metals in pore
waters, but two-dimensional structure in concentration profiles has demon-
strated the potential importance of sedimentary microniches for metal
142 Chapter 3
remobilization.
119,121
The increasing sophistication of the DGT technique is
now also permitting comparisons of measured metal speciation in fresh-
waters with model (e.g. WHAM, ECOSAT) predictions.
122,123
Finally, it should be noted that sediment cores continue to be used to
investigate historical perspectives of environmental contamination by
anthropogenic organic compounds, such as organochlorine pesti-
cides,
124,125
polychlorinated biphenyls,
124,125
polychlorinated naphtha-
lenes,
126
polycyclic aromatic hydrocarbons,
124,127,128
aliphatic hydro-
carbons,
128,129
polychlorinated dibenzo-p-dioxins,
130
polychlorinated
dibenzofurans,
130
and polybrominated diphenyl ethers
125,131
in environ-
ments as diverse as the Great Lakes
124,129–131
and Washington
128
in
North America, Esthwaite Water
126
in England, remote mountain
lakes
127
in the Pyrenees and Alps in Europe and Greenland.
125
3.3.3.3 Onondaga Lake. Onondaga Lake, near Syracuse, New York
State, has been called ‘one of the world’s most polluted lakes’ and
provides a textbook case of the impact of industrial processes on the
environment.
132
Rich natural resources, especially the local brine
springs, made the Syracuse region an ideal location for chemical
manufacturing. Unfortunately, the exploitation of these, despite the
implementation of significant technological advances and, for the time,
environmentally responsible operation of factories had a devastating
impact upon the chemistry of the lake.
The Solvay Process, which was introduced for the manufacture of the
industrially important chemical, ‘soda ash’, i.e. sodium carbonate
(Na
2
CO
3
), along the west shore of Onondaga Lake in 1884, was cheaper
and less polluting than the existing Leblanc Process. Essentially, it made
use of two cheap and plentiful naturally occurring substances in the area
– NaCl from the deep brine springs and CaCO
3
from limestone out-
croppings – in a simple reaction, which yielded two useful products.
CaCO
3
þ 2NaCl "Na
2
CO
3
þ CaCl
2
(3.105)
In practice, this overall reaction required a series of individual reactions
and chemical intermediates, one of the most important involving
ammonia in a step to separate NaHCO
3
from NH
4
Cl by fractional
crystallization at 273 K.
NH
3(g)
þ CO
2(g)
þ NaCl
(ag)
þ H
2
O
(1)
"NaHCO
3(s)
þ NH
4
Cl
(aq)
(3.106)
The NaHCO
3
was subsequently heated to yield Na
2
CO
3
while NH
3
, the
most expensive compound used, was regenerated from the decomposition
of NH
4
Cl. So the very efficient Solvay Process, one of the first industrial
143 Chemistry of Freshwaters
processes to regenerate intermediates, maximized profits and, in theory,
prevented environmental harm from unwelcome discharges.
Unfortunately, however, sales of CaCl
2
from the Onondaga Lake
plant failed to match those of Na
2
CO
3
, with the result that excess CaCl
2
was allowed to be released into a tributary of the lake. In addition,
substantial quantities of unmarketable salts (mainly CaCl
2
) from the
Solvay Process were dumped daily into the lake. Furthermore, waste
slurries pumped into diked beds along the lake shoreline resulted in
substantial leaching of Ca
21
, Na
1
, and Cl
À
ions into the lake by
rainwater runoff. The Ca
21
ions reacted with CO
3

ions, resulting from
H
2
O
(1)
þ CO
2(g)
"H
2
CO
3(aq)
"2H
þ
(aq)
þ CO

3 (aq)
(3.107)
to precipitate CaCO
3
via
Ca

(aq)
þ CO

3(aq)
"CaCO
3(s)
(3.108)
The effect of the deposition of CaCO
3
, at up to 1.7 Â 10
4
t per year, was
to increase the sedimentation rate of the lake several-fold, with a large
CaCO
3
delta where the major tributary, Ninemile Creek, flows into the
lake, and create a layer of CaCO
3
about 1 m thick over the bottom
sediments. As a result, Onondaga Lake became effectively a saturated
solution of CaCO
3
, with a pH of 7.6–8.2, and, most unusually for a lake
in the north-eastern USA, immune to both acid precipitation and
phosphate-induced eutrophication, the latter largely being avoided as
a consequence of
3Ca

(aq)
þ 2PO

4 (aq)
"Ca
3
(PO
4
)
2(s)
(3.109)
Since the closure of the Solvay Plant in 1980, the water quality has
improved as salt concentrations have decreased from 3500 to 1000 mg L
À1
.
The other major industrial process which has polluted Onondaga
Lake has been the production of sodium hydroxide (NaOH) and
chlorine, two of the world’s most important chemicals, from sodium
chloride via the electrolysis of NaCl solution and subsequent amalgama-
tion of the sodium metal produced with the mercury cathode [i.e.
Na(Hg)], prior to spraying into water to yield NaOH. With a single
electrolysis cell containing up to 4 t Hg and a single plant containing
dozens of cells, the escape of mercury (e.g. through leakage) at a rate of
5–10 kg per day from 1946–1970 into the lake resulted in mercury-
contaminated sediments (440 mg kg
À1
) and fish, much of the mercury
in the latter being in the form of the highly toxic CH
3
Hg
1
. Despite the
closure of the chlor-alkali plant in the late 1980s, mercury is still flowing
into the lake from tributaries, although concentrations of soluble
144 Chapter 3
mercury compounds in the lake are declining.
132
Kim and co-workers
133
have simulated mercury transport and speciation (Hg
II
, Hg
0
, CH
3
Hg
1
)
in both the water column and the benthic sediment using a Water
Quality Simulation Program. Model predictions generally agreed with
measured values for the water column, in which advection, sorption, and
settling were important mechanisms for mercury transport. Reduction,
methylation, and demethylation affected mercury speciation in the water
column and the benthic sediment. Natural attenuation showed no
positive impact for remediation when compared with dredging and
capping.
3.3.4 Nutrients in Water and Sediments
3.3.4.1 Phosphorus and Eutrophication. Eutrophication can be con-
sidered as the excessive primary production of algae and higher plants
through enrichment of waters by inorganic plant nutrients, usually
nitrogen and phosphorus. The latter, in the form of phosphate, is
normally the limiting nutrient because the amount of biologically
available phosphorus is small in relation to the quantity required for
algal growth.
134
Sources of nutrients can be discrete (e.g. specific sewage
outfall) or diffuse (e.g. farmland fertilizers). Eutrophic lakes, highly
productive and often turbid owing to the presence of algae, can be
contrasted with oligotrophic lakes, which exhibit low productivity and
are clear in summer. There have been many examples of unsightly algal
blooms affecting freshwater bodies throughout the world, from Lake
Erie in North America to the Norfolk Broads in East Anglia, England.
59
Public concern has increased along with the reported incidences of
toxicity of the bloom-forming organisms, in particular the cyanobacter-
ia (blue-green algae), which have been implicated in fish fatalities, for
example in Loch Leven, Scotland.
135
The environmental damage costs
of freshwater eutrophication in England and Wales have been estimated
at d75–114.3 M per year.
136
The chemical form of phosphorus in the water column available for
uptake by biota is important. The biologically available phosphorus is
usually taken to be ‘soluble reactive phosphorus (orthophosphate)’, i.e.
which, upon acidification of a water sample, reacts with added molyb-
date to yield molybdophosphoric acid, which is then reduced with SnCl
2
to the intensely-coloured molybdenum blue complex and is determined
spectrophotometrically (l
max
¼ 882 nm).
137
Reduction in inputs of
phosphate, for example from point sources or by creating water
meadows and buffer strips to contain diffuse runoff, has obviously been
one of the major approaches to stemming eutrophication trends and
145 Chemistry of Freshwaters
encouraging the restoration of affected lakes. That this has not always
been successful, however, can be attributed in many cases to the release/
recycling of phosphorus previously deposited to and incorporated with-
in the bottom sediments of the lake systems in question.
138
The potential mobility and bioavailability of sedimentary phosphorus
are to a large extent governed by the chemical associations and interac-
tions of phosphorus with different sedimentary components.
139
Bearing in
mind the removal or transport of phosphorus to the sediments, especially
important phases are likely to be ‘organic phosphorus’ from deposited,
dead, decaying biota, and ‘sorbed orthophosphate’ on inorganic particu-
lates (e.g. iron (hydr)oxides). Many sequential extraction schemes have
been developed to investigate phosphorus fractionation in lake sediments.
Perhaps the most sophisticated is that of Psenner et al.
140
who identify,
operationally define, and separate the following fractions: ‘labile, loosely
bound or adsorbed’ (NH
4
Cl-extractable); ‘reductant-soluble, mainly from
iron hydroxide surfaces’ (buffered dithionite-extractable); ‘adsorbed to
metal oxides (e.g. Al
2
O
3
)’ (NaOH-extractable), subsequently distinguish-
able from ‘organic’ (also NaOH-extractable); ‘apatite-bound’ (HCl-ex-
tractable); and ‘residual’ (persulfate-digestible). Pardo and co-workers
141
have reviewed such approaches in the light of the development by the
European Commission of a harmonized protocol for the fractionation of
sedimentary phosphorus.
Many such studies of sedimentary phosphorus profiles, also incorpor-
ating pore water measurement of soluble reactive phosphate, have
demonstrated that redox-controlled dissolution of iron (hydr)oxides
under reducing conditions at depth releases orthophosphate to solution.
This then diffuses upwards (and downwards) from the pore water
maximum to be re-adsorbed or co-precipitated with oxidized Fe
III
in
near-surface oxic sections. The downwards decrease in solid phase
‘organic’ phosphorus indicates increasing release of phosphorus from
deposited organic matter with depth, some of which will become
associated with hydrous iron and other metal oxides, added to the pool
of mobile phosphorus in pore water or contribute to ‘soluble unreactive
phosphorus’. The characteristic reactions involving inorganic phos-
phorus in the sediments of Toolik Lake, Alaska, are shown in
Figure 7.
142
If, at depth, the concentrations of Fe
21
and phosphate are
high enough, authigenic vivianite (Fe
3
(PO
4
)
2
.8H
2
O) may precipitate out.
With redox control largely responsible for phosphorus mobility in
sediments, what might the consequences of oxygen depletion in the
hypolimnion be? If conditions in the surface sediments are not suffi-
ciently oxidizing to precipitate iron (hydr)oxides and thereby adsorb the
phosphate (i.e. the redox boundary for iron may be in the overlying
146 Chapter 3
water column), the phosphate from previously deposited sediments
would stream off into the water column and promote eutrophication.
This process is called internal loading of phosphorus.
Redox control may not be the only process affecting release of
phosphorus from sediments. During the enhanced photosynthesis of
algal blooms, the pH of lake water increases as CO
2
is used up and
HCO
3
À
increases. Thus, in summer, both Lough Neagh
143
in N. Ireland
and Lake Glanningen
144
in Sweden have shown an increase in water
Figure 7 Characteristic reactions involving phosphorus in the sediments of Toolik Lake,
Alaska. The primary processes controlling porewater phosphorus concentrations
are adsorption to and desorption from iron oxyhydroxides and the precipitation
of authigenic vivianite
(Reprinted with permission from ref 142, r E. Schweizerbart’sche Verlags-
buchhandlung, 1987)
147 Chemistry of Freshwaters
phosphate concentration. It seems likely that OH
À
is exchanging with
sorbed phosphate in alkaline lakes, thus releasing phosphorus from
association with iron and aluminium (hydr)oxides (see Section 3.2.4.3).
If the waters are calcium-rich, however, this could have the effect of
precipitating phosphate as hydroxyapatite (Ca
10
(PO
4
)
6
(OH)
2
) under the
high-pH conditions prevailing. There can be other factors, such as
temperature, which promote phosphorus release. An increase in tem-
perature can lead to increased bacterial activity, which increases oxygen
consumption and decreases the redox potential. Turbulence may also be
a factor. For example, wind-induced bottom currents in shallow lakes
could destroy any pH gradients across a buffered sediment-water inter-
face and re-suspend P-rich sediment in water of high pH.
145
There have been many proposals for restoration of eutrophic lakes.
146
For example, 34 options have been put forward for Loch Leven,
147
Scotland, with the aim of reducing algal biomass and the incidence of
the bloom-forming cyanobacteria in particular. These strategies fall into
two categories: (i) those aimed at stemming the production of algae in
the first place, including reduction in the supplies of light and nutrients
and (ii) those aimed at reducing existing algal biomass, including
physical methods such as increased flushing of the loch and harvesting
of blooms, chemical treatment with algicides, and biological methods
involving viruses, parasitic fungi and grazing protozoans, rotifers, and
micro-crustaceans. Thus far, progress has largely been restricted to
reducing external inputs of phosphorus from point sources to the loch,
an approach which could perhaps be supplemented by the creation of
water meadows and/or buffer strips to reduce inputs from diffuse runoff.
Elsewhere, there was a surge in wetlands construction in the 1980s, using
a mixture of plants to clean water contaminated with nitrates and
phosphates.
148
One of the largest wetlands restoration projects is
planned for the Florida Everglades, to the south and east of the rich
farmlands around Lake Okeechobee, where runoff waters enriched in
phosphorus from fertilizers have disrupted the flora and fauna. As water
flows through cattails and sawgrass, phosphorus concentrations are
expected to decline from 170 to 50 mg L
À1
. An intriguing attempt to
use ochre (cf. Section 3.3.1.3), discharged from abandoned mines, to
strip phosphate from sewage and agricultural runoff and then use the
phosphate-saturated ochre as a slow-release phosphate fertilizer to
fertilize a range of grasses and cereal crops has been reported.
149
It
should be noted that the addition of ferric sulfate or chloride to mop up
phosphate in eutrophic lakes
59
may not work in the long term as there
may be subsequent release of deposited phosphate from sediments under
reducing conditions.
148 Chapter 3
A novel use of phosphate to counter acidification has emerged in
recent years.
150
Traditional remedial methods which have been adopted
include the direct liming of lakes, e.g. in Sweden,
151
or of catchments,
e.g. around Loch Fleet in SW Scotland.
152
Although helpful, such
approaches based on neutralization are costly and usually need to be
repeated at regular intervals. Furthermore, the resulting Ca-rich waters
may turn out to support biota quite different from those found in
natural softwater lakes. An alternative approach has been tried by
Davison and co-workers on Seathwaite Tarn, an upland reservoir in
the English Lake District.
131
Phosphate fertilizer was added to stimulate
primary productivity and thereby increase the assimilation of nitrate.
This generates base according to the equation
106CO
2(g)
þ138H
2
Oþ16NO
À
3
"(CH
2
O)
106
(NH
3
)
16
þ16OH
À
þ138O
2(g)
(3.110)
As concentrations of nitrate are increasingly high in acid waters, the
addition of modest amounts of phosphate may generate sufficient base
to combat acidity without inducing excessive productivity. An increase
in pH of 0.5 and a marked increase in biological productivity at all levels
were observed over the three-year period of the experiment. In the
longer term, additional quantities of base should be generated by the
anoxic decomposition of organic material accumulating on the lake-bed
(through the dissimilative reduction of inorganic oxidants such as
nitrate, sulfate, or iron hydr(oxides) present in the sediments – Equa-
tions (3.100) to (3.103)). If oxygen is the electron acceptor there is no net
gain of base (Equation (3.99)), there is no advantage in adding nitrate
because 1 mol of nitrate is required to generate 1 mol of base, and the
generated base (contributing to alkalinity) should not be confused with
the temporary rise in pH associated with CO
2
consumption, which
affects neither alkalinity nor acidity (see Section 3.2.4.1).
3.3.4.2 Nitrate in Groundwater. Principal sources of nitrate in water
are runoff and drainage from land treated with agricultural fertilizers
and also deposition from the atmosphere as a consequence of NO
x
released from fossil fuel combustion. The nitrogen present in soil
organic matter may also be released as nitrate through microbial action.
Nitrate’s role as a nutrient contributes significantly to blooms of algae,
which upon death are decomposed first by aerobic bacteria, thereby
depriving fish and other organisms of oxygen.
59,147
There has long been concern expressed over the presence of nitrate in
drinking water at concentrations exceeding the EC guideline of 50 mg L
À1
because of the risk of methaemoglobinaemia (blue baby syndrome). Here,
149 Chemistry of Freshwaters
NO
3
À
is reduced in the baby’s stomach to NO
2
À
, which, on absorption,
reacts with oxyhaemoglobin to form methaemoglobin. There have also
been fears over the reaction of NO
2
À
with secondary amines from the
breakdown of meat or protein to produce carcinogenic N-nitroso com-
pounds, but there is as yet no clear evidence of a link between stomach
cancer and nitrate in water.
153
Nevertheless, there is growing concern over
the contamination of groundwater by nitrate, for example in regions such
as the Sierra Pelona Basin, California.
154
There the local groundwaters,
the major source of drinking water from private water wells located near
each private residence in the rural communities, often exceed the USEPA
maximum contaminant level for drinking water of 10 mg L
À1
(NO
3
–N).
Isotopic investigations, based upon
15
N/
14
N, have confirmed the predo-
minance of anthropogenic, organic human, and/or animal waste and
decay of irrigation-enhanced vegetation rather than natural nitrate
sources. In south Dorset, UK, the cause of the increase in the nitrate
concentrations of the Chalk groundwater from a baseline of 1.04 mg L
À1
(NO
3
-N) to 6.37 mg L
À1
has been attributed to increased fertilizer use and
increased livestock numbers, mostly during the final 25 years of the 20th
century.
155
It is feared that nitrate concentrations in both surface and
groundwaters of the Chalk in southern England may approach or exceed
the EC limit of 11.3 mg L
À1
(NO
3
–N) for potable supplies in future years.
Nitrate in manure and fertilizer is also now under suspicion as an
endocrine disruptor (see Section. 3.3.5.2.3).
156
3.3.5 Organic Matter and Organic Chemicals in Water
3.3.5.1 BOD and COD. The solubility of oxygen in water in equili-
brium with the atmosphere at 251C is 8.7 mg L
À1
. Causes of oxygen
depletion include decomposition of biomass (e.g. algal blooms) and the
presence of oxidizable substances (e.g. sewage, agricultural runoff, factory
effluents) in the water. The addition of oxidizable pollutants to streams
produces a typical sag in the dissolved oxygen concentration. The degree
of oxygen consumption by microbially mediated oxidation of organic
matter in water is called the Biochemical (or Biological) Oxygen Demand
(BOD) (cf. Equation (3.99)). Another index is the Chemical Oxygen
Demand (COD), which is determined by using the powerful oxidizing
agent, dichromate (Cr
2
O
7

), to oxidize organic matter
2Cr
2
O

7
þ 3CH
2
O þ 16H
1
"4Cr
31
þ 3CO
2(g)
þ 11H
2
O (3.111)
followed by back-titration of excess added dichromate with Fe
21
Cr
2
O

7
þ 6Fe
21
þ 14H
1
"2Cr
31
þ 6Fe
31
þ 7H
2
O (3.112)
150 Chapter 3
As Cr
2
O
7

oxidizes substances not oxidized by O
2
, the COD is usually
greater than the BOD and to some extent overestimates the threat posed
to oxygen content.
3.3.5.2 Synthetic Organic Chemicals. A large number of organic
compounds are synthesized for agricultural use, mainly as pesticides,
and for industrial use as solvents, cleaners, degreasers, petroleum
products, plastics manufacture, etc.
157
Many organic micropollutants
percolate into the soil and accumulate in aquifers or surface waters.
They can contaminate drinking water sources via agricultural runoff to
surface waters or percolation into groundwaters, industrial spillages to
surface waters and groundwaters, runoff from roads and paved areas,
industrial waste water effluents leaching from chemically treated sur-
faces, domestic sewage effluents, atmospheric fallout, and as leachate
from industrial and domestic landfill sites.
157
In the last few years,
emerging chemical contaminants such as pharmaceuticals and personal
care products have also been detected in freshwaters.
158
In a widely
publicized study, Kolpin and co-workers
159
investigated the occurrence
of pharmaceuticals as well as other organic wastewater contaminants in
a national reconnaissance study of 95 contaminants in 139 streams in 30
states of the USA in 1999–2000. As many as 38 of the 95 targeted
compounds were found in a single water sample, although the average
number of compounds in a given sample was seven and the concentra-
tions of individual compounds were typically much less than 1 mg L
À1
.
Three classes of compounds (detergent metabolites, plasticizers, ster-
oids) had the highest concentrations and the most frequently detected
compounds were coprostanol (faecal steroid), cholesterol (plant and
animal steroid), N,N-diethyltoluamide (insect repellent), tri(2-chlor-
oethyl)phosphate (fire retardant) and 4-nonylphenol (non-ionic deter-
gent metabolite) (Figure 8).
160
Although measured concentrations were
generally low and rarely exceeded drinking water guidelines or aquatic-
life criteria, little is known about the potential interactive effects that
may occur from complex mixtures of organic wastewater contaminants
in the environment.
3.3.5.2.1 Pesticides. Many pesticides in aquifers have resisted degra-
dation and are more likely to persist there because of reduced microbial
activity, absence of light, and lower temperatures.
161
Numerous aqui-
fers, for example in eastern England, have been found to exceed the
Maximum Admissible Concentrations (MAC) guidelines for total pes-
ticides in drinking water (0.5 mg L
À1
), due primarily to the presence of
herbicides of the carboxy acid and basic triazine groups. Gray
157
has
listed the 12 pesticides most often found in UK drinking waters in two
151 Chemistry of Freshwaters
groups, frequently occurring (atrazine, chlortoluon, isoproturon,
MCPA, mecoprop, simazine) and commonly occurring (2,4-D, dicam-
ba, dichlorprop, dimethoate, linuron, 2,4,5-T). A major seasonal source
of insecticide in freshwaters is sheep dipping. With organophosphorus
compounds, which themselves replaced the more persistent organo-
chlorine insecticides such as lindane, now falling out of favour because
of health risks to users, the use of synthetic pyrethroids as alternatives
100
60
40
20
0
40
30
20
10
0
S
t
e
r
o
i
d
s
N
o
n
p
r
e
s
c
r
i
p
t
i
o
n

d
r
u
g
s
I
n
s
e
c
t

r
e
p
e
l
i
e
n
t
D
e
t
e
r
g
e
n
t

m
e
t
a
b
o
l
i
t
e
s
D
i
s
i
n
f
e
c
t
a
n
t
s
P
l
a
s
t
i
c
i
z
e
r
s
F
i
r
e

r
e
t
a
r
d
a
n
t
s
A
n
t
i
b
i
o
t
i
c
s
I
n
s
e
c
t
i
c
i
d
e
s
P
A
H
s
R
e
p
r
o
d
u
c
t
i
v
e

h
o
r
m
o
n
e
s
O
t
h
e
r

p
r
e
s
c
r
i
p
t
i
o
n

d
r
u
g
s
A
n
t
i
o
x
i
d
a
n
t
s
F
r
a
g
r
a
n
c
e
s
S
o
l
v
e
n
t
A
B
F
r
e
q
u
e
n
c
y

o
f

D
e
t
e
c
t
i
o
n

(
%
)
T
o
t
a
l

C
o
n
c
e
n
t
r
a
t
i
o
n

(
%
)
4
5
1
5
3
7
2
22
7
6
11
14
5
2
1
Figure 8 Organic wastewater contaminants by general use category. Emerging organic
contaminants in US streams, as reported by the US Geological Survey
159,160
,
can be broken down into 15 categories. A shows the frequency of detection, and
B shows the fraction of the total measured concentration (%). The number of
compounds in each category is shown above the bars in A
(Reprinted with permission from ref 159, r American Chemical Society,
2002)
152 Chapter 3
has resulted in the death of aquatic organisms in UK rivers. Pyrethroids,
which do not persist in the environment and are largely non-toxic to
mammals, are toxic to invertebrates and are estimated to be at least 100
times more toxic in the aquatic environment than organophosphorus
pesticides. It appears to be the pouring of waste dip into holes in the
ground that has caused the problem.
162
In order to protect the aquatic
environment, the Environment Agency in England assesses water qual-
ity against EQSs. Defined as the concentration of a substance which
must not be exceeded within the aquatic environment in order to protect
it for its recognized uses, EQSs are specific to individual substances,
including pesticides.
Atrazine, now banned in many European countries but which still
accounts for 40% of all herbicide applied in the USA and is most often
applied in the spring, is routinely present in streams, rivers, and
reservoirs at levels of 1–10 mg L
À1
, close to the USEPA standard of 3
mg L
À1
.
163,164
Runoff peaks of 100–200 mg L
À1
, however, have been
recorded at the times when frogs are breeding and tadpoles are devel-
oping. Atrazine is therefore suspected of causing the gonadal abnorm-
alities, such as retarded development and hermaphroditism, found in
male wild leopard frogs in different regions of the USA.
163
(cf. Section
3.3.5.2.3)
3.3.5.2.2 Polychlorinated biphenyls (PCBs). The Great Lakes, the
largest body of freshwater in the world, with long hydraulic residence
times, long food chains, and multiple sources of PCBs, have been the focal
point of PCB research in aquatic systems. The distribution of PCBs
between the dissolved and particulate phases is dependent on the con-
centration of suspended particulate matter, dissolved and particulate
organic carbon concentrations, and the extent to which the system is at
equilibrium. In the 1990s, water concentrations of up to 0.6 ng L
À1
were
observed in the most contaminated lakes (Michigan, Erie, and Ontario),
which may be compared with the USEPA Great Lakes Water Quality
Guidance criteria of 0.017 ng L
À1
. Sediment concentrations peaked in the
1970s, the period of maximum PCB production in the USA. Following a
ban upon their North American production during the 1970s, there was a
significant decline in the PCB concentrations of Great Lakes’ fish from
the mid-1970s to the mid-1980s but the rate of decrease has since slowed
or stopped for all lakes.
165
In common with other organochlorine
compounds, it is the stability, persistence, volatility, and lipophilicity of
PCBs, which lead to considerable biomagnification along the food chain,
often far from the place of release. To these traditional halogenated
contaminants can now be added fire-retardant polybrominated diphenyl
153 Chemistry of Freshwaters
ethers (PBDEs),
166
and perfluorooctane sulfonates (PFOS),
167
which have
been found in Great Lakes’ water and biota.
3.3.5.2.3 Endocrine disruptors. Concern has recently been expressed
over the possible role of various synthetic organic chemicals (e.g.
organochlorine pesticides, PCBs, phthalates, alkylphenolethoxylates
(APEs), alkylphenols, etc.) as disruptors of endocrine systems of wildlife
and perhaps even of humans.
168,169
Reproductive changes in male
alligators from Lake Apopka, Florida, embryonic death, deformities,
and abnormal nesting behaviour in fish-eating birds in the Great Lakes
region and the occurrence of hermaphroditic fish near sewage outfalls on
some British rivers have been attributed to postulated oestrogenic or
anti-androgenic effects of some of these chemicals.
168,169
Most APEs,
which are used as detergents, emulsifiers, wetting agents, and dispersing
agents, enter the aquatic environment after disposal in wastewater.
During biodegradation treatment of the latter, the APEs are trans-
formed into more toxic, short-chain ethoxylates, alkylphenol carboxylic
acids, and alkylphenols.
170
The threshold concentration of nonylphenol
in water for production of the female egg yolk protein, vitellogenin, in
male rainbow trout is B10 mg L
À1
.
171
It also appears that nonylphenol
concentrations in many European rivers are up to 10 times higher than
those found in USA rivers, which are typically o1 mg L
À1
,
170,172
the EU
limit. It has been suggested, however, that natural oestrogens (e.g.
oestrone and 17b-oestradiol) may be responsible for the observed effects,
perhaps after conversion of inactive excreted metabolites to active forms
by bacterial enzyme action during sewage treatment.
173
The COMPRE-
HEND (Community Programme of Research on Environmental Hor-
mones and Disruptors) 1999–2001 survey found that in some domestic
sewage effluents there were oestrogenic steroids present, almost certainly
from human excretion, at concentrations sufficient to account for most
of the oestrogenicity, causing widespread sexual disruption, in fish in
rivers throughout England and Wales.
174
Maximum measured concen-
trations were 14 ng L
À1
for oestradiol, 51 ng L
À1
for its principal
metabolite oestrone, 17 ng L
À1
for another metabolite oestriol, and 2 ng
L
À1
for the synthetic steroid ethinylestradiol, the active ingredient in the
birth control pill. As a result, the Environment Agency has set a
threshold exposure limit for steroid estrogens of 1 ng L
À1
for oestradiol,
3 ng L
À1
for oestriol and 0.1 ng L
À1
for ethinylestradiol in sewage
effluent.
175
In industrial effluents, the oestrogenic steroids were not
detected but nonylphenol (NP), NP mono- and diethoxylates, and
bisphenol-A were found at concentrations up to 3, 7, and 1 mg L
À1
,
respectively.
174
The relatively high hydrophobicity of alkylphenols has
154 Chapter 3
led to their accumulation in sludge at activated sludge treatment
works.
176
3.3.5.2.4 Pharmaceuticals and personal care products (PPCPs). In
Europe, B3000 different substances are used in medicines such as
painkillers, antibiotics, contraceptives, beta-blockers, lipid regulators,
tranquilizers, and impotence drugs, and there are also thousands of
personal care products (e.g. sunscreens, cosmetics, shampoos, etc.).
177
Municipal wastewater is one of the main entry routes of pharmaceuticals
into the environment. Ternes
158
began monitoring for pharmaceuticals
in Germany in the mid-1990s. Since then, in Switzerland, the detection
of macrolide antibiotics, among the most important anti-bacterial
agents used, in wastewater treatment plants and in the Glatt Valley
Watershed has demonstrated that they are not eliminated completely in
the treatment plants and that residual amounts reach receiving
waters.
178
Also in Switzerland, chemicals from personal care products
containing UV filters, such as benzophenone-3, 4-methylbenzylidene
camphor (4-MBC), and ethyl-hexyl methoxy cinnamate (EHMC), have
been found in untreated wastewater (maximum concentration 19 mg
L
À1
, EHMC), treated wastewater (max. 2.7 mg L
À1
, 4-MBC) and, at
much lower concentrations, lakes and rivers (o2–35 ng L
À1
).
179
In the
UK, Ashton and co-workers
180
investigated the environmental trans-
port of 12 human pharmaceuticals to streams and found that while 10
were detected in sewage treatment works effluent samples (e.g. ibuprofen
in 84% of samples, median concentration 3086 ng L
À1
), there were fewer
and at lower concentrations in streams (e.g. ibuprofen in 69% of
samples, median concentration 826 ng L
À1
).
In the USA, where similar studies have been carried out in treated waters
and streams,
159,181–183
Stackelberg and co-workers
184
have demonstrated
that many of the PPCPs can survive conventional drinking-water-treatment
and occur in potable water supplies. Although concentrations in finished
water were low (93%o0.5mg L
À1
) and the maximum possible lifetime
intake of, for example, carbamazepine would be only 13 mg, compared
with a single therapeutic dose of B100 mg, little is known about potential
health effects associated with chronic ingestion via drinking water.
It is not yet known whether the relatively low environmental concen-
trations found for PPCPs produce adverse effects on aquatic and terres-
trial biota or whether the toxicity of complex mixtures might be totally
different from that of individual compounds.
177
Consideration should
also be given to metabolites excreted by humans and to biological
degradates at treatment plants and elsewhere in the environment.
184,185
Many pharmaceuticals are conjugated with glucuronic acid or sulfate
155 Chemistry of Freshwaters
prior to excretion, but these may be cleaved in wastewater treatment
plants, releasing active pharmaceuticals.
177
Similarly, the disposal of
contaminated sludge on land as a fertilizer should be viewed with
concern.
177
The use of veterinary medicines may also cause environmental
risks.
186
3.3.5.2.5 Industrial solvents. Six are widely used in the UK – di-
chloromethane (DCM), trichloromethane, 1,1,1-trichloroethane (TCA),
tetrachloromethane trichloroethene (TCE), tetrachloroethene or per-
chloroethylene (PCE).
157
Although there has been a steady decrease in
use over the past 20 years, four (TCE, PCE, TCA, and DCM) are
frequently found in drinking water. The major pollution threat is when
solvents are discharged directly into or onto the ground, due to illegal
disposal or accidental spillage. Since groundwater is not exposed directly
to the atmosphere, the solvents are not able to escape by evaporation, so
it is the aquifers that are most at risk from these chemicals. Pollution of
groundwater by industrial solvents is a very widespread problem (e.g.
Netherlands, Italy, USA, UK
187
), with aquifers underlying urbanized
areas such as Milan, Birmingham, London, or New Jersey containing
high concentrations of all solvents. The stability of TCE in particular
and the inability of these solvents to readily evaporate mean that such
contamination will last for many decades.
157
A typical example of groundwater contaminated by synthetic organic
chemicals from jet fuel and degreasing solvents (e.g. halogenated
methanes, ethanes, and ethenes, including trichloroethylene, perchlor-
oethylene, and vinyl chloride) can be found at Otis Air Force Base on
Cape Cod, Massachusetts, USA, where the Cape’s sole-source aquifer
has been affected. The groundwater plumes, some in excess of 5 km in
length, moving at B0.5 m per day, contaminate 30 million litres of the
Cape’s drinking water every day. Reactive wall (Ni–Fe) technology is
being employed to try to reduce concentrations of 5–150 mg L
À1
TCE
and tetrachloroethylene below the local drinking water limits of 0.5 mg
L
À1
.
188
The chlorinated ethenes are degraded in the presence of zero-
valent iron by an abiotic reduction process.
3.3.5.2.6 MTBE. Methyl tert-butyl ether (MTBE), an oxygen-con-
taining compound used as a fuel additive since the 1970s, moves quickly
through soil, is highly soluble and does not biodegrade easily. It has
been found in shallow groundwater in Denver, New England,
189
and
elsewhere in the USA, most notably in Santa Monica, California, where
a 1996 spill of MTBE-containing gasoline resulted in the contamination
of wells at concentrations as high as 610 mg L
À1
, well above the state’s
advisory limit of 35 mg L
À1
.
190
In a preliminary assessment of the
156 Chapter 3
occurrence and possible sources of MTBE in groundwater in the United
States in 1993/1994, as part of the US Geological Survey’s National
Water-Quality Assessment programme, Squillace and co-workers
191
found that, out of 60 volatile organic chemicals determined, MTBE
was the second most frequently detected chemical in samples of shallow
ambient groundwater from urban areas. MTBE was detected above 0.2
mg L
À1
in 17% of shallow groundwater samples from urban areas, 1.3%
of shallow groundwater from agricultural areas, and 1.0% of deeper
groundwater samples from major aquifers. Only 3% of the shallow wells
sampled in urban areas had MTBE concentrations 420 mg L
À1
, the
estimated lower limit of the USEPA draft drinking water health
advisory. The 1999 Report of the Blue Ribbons Panel on oxygenates
in gasoline found that 5–10% of community drinking water supplies in
high-MTBE-use areas showed at least detectable concentrations of
MTBE, with 1% 420 mg L
À1
.
192
As MTBE generally was not found,
in shallow urban groundwater, along with benzene, toluene, ethylben-
zene, or xylene, which are commonly associated with petrol spills, it was
concluded that possible sources of MTBE in groundwater include
leaking storage tanks and non-point sources such as recharge of
precipitation and storm water runoff. In the summer of 1999, 13
municipal wells on the south shore of Lake Tahoe, located close to
commercial areas with gasoline stations, were shut down as a result of
actual or threatened MTBE contamination.
193
In Meyers, an unknown
amount of gasoline leaked from a pipe into the soil for about two weeks
before the release was repaired and five months later a groundwater
sample collected at the gasoline station was 28,000 mg L
À1
in MTBE.
193
As MTBE is thought to be potentially carcinogenic to humans, its use
poses an interesting dilemma for regulators, given that it helps to reduce
carbon monoxide emissions from cars. Regardless of what happens to
MTBE use in the future, it is clear that significant amounts of this
compound are already present in the sub-surface.
192
In Europe, how-
ever, the problem seems much less severe.
194,195
QUESTIONS AND PROBLEMS
(i) Calculate the ionic strength of a solution which is 0.01 mol L
À1
with respect to potassium sulfate and 0.002 mol L
À1
with respect
to magnesium chloride. Use this value of ionic strength and the
Gu¨ ntelberg approximation to determine the mixed acidity con-
stant, K
0
, for methanoic acid (K ¼ 10
À3.75
).
(ii) Construct a plot to show how Àlog{activity} varies with pH for
all species in one litre of groundwater containing 3 Â 10
À4
moles
157 Chemistry of Freshwaters
of 4-chlorophenol (K
0
¼ 10
À9.18
). Annotate the plot to show the
equilibrium pH of the groundwater.
(iii) Calculate the equilibrium pH of rainwater in equilibrium with
CO
2(g)
at a partial pressure of 0.00035 atm (hint: the charge
balance equation can be approximated by {H
1
} ¼ {HCO
3
À
}).
log Kð288 KÞ
CO
2ðgÞ
þ H
2
O Ð H
2
CO
Ã
3
À1:34
H
2
CO
Ã
3
Ð H
þ
þ HCO
À
3
À6:35
HCO
À
3
Ð H
þ
þ CO

3
À10:33
(iv) Construct a pe–pH diagram for selenium species present in
natural waters. Assume that the total dissolved concentration
of selenium is 10
À6
mol L
À1
. From the diagram, predict the
major selenium species in
(i) oxic and acidic waters (peB10, pH 4–7)
(ii) oxic and alkaline waters (peB10, pH 47)
(iii) anoxic groundwaters (peBÀ3, pH 4–8).
For each set of conditions, outline the implications for sorption
onto solid phases.
log K(298 K)
SeO

4
þ 4H
þ
þ 2e
À
Ð H
2
SeO
3
þ H
2
O 41.40
SeO

4
þ 3H
þ
þ 2e
À
Ð HSeO
À
3
þ H
2
O 38.76
SeO

4
þ 2H
þ
þ 2e
À
Ð SeO

3
þ H
2
O 30.26
H
2
SeO
3
Ð HSeO
À
3
þ H
þ
À2.75
HSeO
À
3
Ð SeO

3
þ H
þ
À8.50
H
2
SeO
3
þ 4H
þ
þ 4e
À
Ð Se
ðsÞ
þ 3H
2
O 48.58
HSeO
À
3
þ 5H
þ
þ 4e
À
Ð Se
ðsÞ
þ 3H
2
O 51.33
SeO

3
þ 6H
þ
þ 4e
À
Ð Se
ðsÞ
þ 3H
2
O 59.83
Se
ðsÞ
þ 2H
þ
þ 2e
À
Ð H
2
Se
ðaqÞ
À3.52
Se
ðsÞ
þ H
þ
þ 2e
À
Ð HSe
À
À7.32
H
2
Se Ð HSe
À
þ H
þ
À3.80
(v) Draw, describe, and compare the concentration profiles of the
chemical species of manganese, iron, arsenic, and phosphorus
likely to be found in the solid and solution phases of unmixed
sediments at the bottom of a seasonally anoxic, eutrophic
freshwater lake during (i) summer and (ii) winter.
158 Chapter 3
(vi) With respect to human health and ecological impact, discuss
the short- and long-term consequences of the products of the
synthetic organic chemical industry upon the quality of surface
waters and groundwaters.
(vii) Explain the chemistry underlying (i) the major detrimental
effects of metal mining upon rivers and groundwaters and (ii)
associated preventive or remedial measures.
(viii) Critically discuss the effectiveness of measures to counter the
effects of (i) acidification and (ii) eutrophication in freshwater
lakes.
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Survey, NERC, Keyworth, 1998.
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A.J. Horne, Limnology, 2nd edn, McGraw-Hill, New York, 1994.
D. Langmuir, Aqueous Environmental Geochemistry, Prentice-Hall,
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F.M. Morel and J.G. Hering, Principles and Applications of Aquatic
Chemistry, Wiley, New York, 1993.
J. Pankow, Aquatic Chemistry Concepts, Lewis, Michigan, 1991.
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169 Chemistry of Freshwaters
CHAPTER 4
Chemistry of the Oceans
STEPHEN J. DE MORA
International Atomic Energy Agency, Marine Environment Laboratory,
4 quai Antoine 1
er
, MC 98000, Principality of Monaco
4.1 INTRODUCTION
The World Ocean is a complex mixture containing all the elements, albeit
in dilute amounts in some cases. Seawater contains dissolved gases and,
apart from some exceptional environments, is consequently both well
oxygenated and buffered at a pH of about 8. There are electrolytic salts,
the ionic strength of seawater being approximately 0.7, and many organic
compounds in solution. At the same time, there is a wide range of
inorganic and organic particles in suspension. However, these comforta-
ble distinctions become quite confused in seawater because some mole-
cules present in true solution are sufficiently large to be retained by a filter.
Moreover, surface adsorption allows particles to scavenge-dissolved ele-
ments and accumulate coatings of organic material from solution. Some
elements, particularly those with biochemical functions, may be rapidly
removed from solution. Concurrently, reactions involving geological time
scales are proceeding slowly. Yet despite this apparent complexity, many
aspects of the composition of seawater and chemical oceanography can
now be explained with recourse to the fundamental principles of chem-
istry. This chapter serves to bridge the gap between those with environ-
mental expertise and those with a traditional chemical background.
4.1.1 The Ocean as a Biogeochemical Environment
A traditional approach utilised in geochemistry, and now also in envi-
ronmental chemistry, is to consider the system under investigation a
reservoir. For a given component, the reservoir has sources (inputs) and
sinks (outputs). The system is said to be at equilibrium, or operating
170
under steady-state conditions, when a mass balance between inputs and
outputs is achieved. An imbalance could signify that an important
source or sink has been ignored. Alternatively, the system may be
perturbed, possibly mediated through anthropogenic activities, and
therefore be changing towards a new equilibrium state.
Processes within the reservoir that affect the temporal and spatial
distribution of a given component are transportation and transforma-
tions. Both physics and biology within the system play a role. Clearly,
transport effects are dominated by the hydrodynamic regime. Although
transformations involve both chemical (dissolution, redox reactions,
speciation changes) and geological (sedimentation) processes, biological
activity generally controls nutrient and trace metal distributions. Fur-
thermore, the biota influences concentrations of O
2
and CO
2
, which in
turn determine the pH and pe (i.e., the redox potential), respectively. For
these reasons, some fundamental aspects of descriptive physical and
biological oceanography are included in this chapter.
In terms of biogeochemical cycling, the ocean constitutes a large
reservoir. The surface area is 361.11 × 10
6
km
2
, encompassing nearly
71% of the earth’s surface. The average depth is 3.7 km, but depths in
the submarine trenches can exceed 10 km. The ocean contains about
97% of the water in the global hydrological cycle. A schematic repre-
sentation of the oceanic reservoir is presented in Figure 1. The material
within it can be operationally defined, usually based on filtration, as
dissolved or particulate. For simplicity here, the ocean is divided into
two layers, with distinct surface and deepwaters. The boundary regions
are also distinguished, as the composition in these regions can be quite
different to that of bulk seawater. Furthermore, interactions within
these environments can alter the mass transfers across the boundary.
The rationale for such features will be presented in subsequent sections.
Material supplied to the ocean originates from the atmosphere, rivers,
glaciers and hydrothermal waters. The relative importance of these path-
ways depends upon the component considered and geographic location.
River runoff commonly constitutes the most important source. Trans-
ported material may be either dissolved or particulate, but discharges are
into surface waters and confined to coastal regions. Hydrothermal waters
are released from vents on the seafloor. Such hydrothermal waters are
formed when seawater circulates into the fissured rock matrix, and under
conditions of elevated temperature and pressure, compositional changes in
the aqueous phase occur due to seawater – rock interactions. This is an
important source of some elements, such as Li, Rb and Mn. The atmos-
phere supplies particulate material globally to the surface of the ocean. In
recent years, this has been the most prominent pathway to the World
171 Chemistry of the Oceans
Ocean for Pb, identified by its isotopic signature as originating from petrol
additives. Wind-borne transport is greatest in low latitudes and the Sahara
Desert is known to act as an important source of dust. Also, the airborne
flux of nutrients, notably nitrogenous compounds, has become increasingly
recognised as important both in some coastal waters, such as Chesapeake
Bay, and large seas, including the Mediterranean Sea. In contrast, glacial
activity makes little impact on the World Ocean. Glacier-derived material
tends to be comprised of physically weathered rock residue, which is
relatively insoluble. In addition, the input is largely confined to Polar
Regions, with Antarctica responsible for approximately 90% of the
material.
Although volatilisation and subsequent evasion to the atmosphere can be
important for elements, such as Se and Hg that undergo biomethylation,
Figure 1 A schematic representation of the ocean reservoir. The source and sink fluxes are
designated as g and n, referring to gross and net fluxes, thereby indicating that
interactions within the boundary regions can modify the mass transfer. Within
seawater, the p " d term signifies that substances can undergo particulate–
dissolved interactions. However, it must be appreciated that several transporta-
tion and transformation processes might be operative
(Adapted from Chester, 1990.
1
)
172 Chapter 4
sedimentation acts as the major removal mechanism. The mechanism is a
geological/physical process, essentially the deposition of suspended parti-
cles in response to changes in the hydrodynamic regime. Such removal is
especially important in coastal environments. Marine organisms play an
important role in the open sea through the sinking of shells of microor-
ganisms and faecal pellets. The chemical precipitation of salts from seawa-
ter occurs only under special conditions. CaCO
3
can precipitate in warm
tropical lagoons and Mn
21
can be oxidised to the relatively insoluble
MnO
2
, a process of importance near deep-sea hydrothermal vents.
Some definitions help in the interpretation of chemical phenomena in
the ocean. Conservative behaviour signifies that the concentration of a
constituent or absolute magnitude of a property varies only due to
mixing processes. Components or parameters that behave in this manner
can be used as conservative indices of mixing. Examples are salinity and
potential temperature, the definitions for which are presented in subse-
quent sections. In contrast, non-conservative behaviour indicates that
the concentration of a constituent may vary as a result of biological or
chemical processes. Examples of parameters that behave non-conserv-
atively are dissolved oxygen and pH.
Residence time, t, is defined as
t =
A
dA=dT ( )
(4:1)
where A is the total amount of constituent A in the reservoir and dA/dT
can be either in rate of supply or the rate of removal of A. This
represents the average lifetime of the component in the system and is,
in effect, a reciprocal rate constant (his concept is discussed further in
Chapter 7).
The photic zone refers to the upper surface of the ocean in which
photosynthesis can occur. This is typically taken to be the depth at
which sunlight radiation has declined to 1% of the magnitude at the
surface. This might typically be 4100 m for visible light or photosyn-
thetically active radiation (PAR), but generally o20 m for UV wave-
lengths, of recent interest due to the enhanced input invoked by
stratospheric ozone depletion.
4.1.2 Properties of Water and Seawater
Water is a unique substance, with unusual attributes because of its struc-
ture. The molecule consists of a central oxygen atom with two attached
hydrogen atoms forming a bond angle of about 1051. As oxygen is more
173 Chemistry of the Oceans
electronegative than hydrogen, it attracts the shared electrons to a greater
extent. In addition, the oxygen atom has a pair of lone orbitals. The overall
effect produces a molecule with a very strong dipole moment, having
distinct negative (O) and positive (H) ends. While there are several impor-
tant consequences, two will be considered here. Firstly, the positive H
atoms of one molecule are attracted towards the negative O atom in
adjacent molecules giving rise to hydrogen bonding. This has important
implications with respect to a number of physical properties, especially
those relating to thermal characteristics. Secondly, the large dipole moment
ensures that water is a very polar solvent.
Considering firstly the physical properties, water has much higher
freezing and melting points than would be expected for a molecule of
molecular weight 18. Water has high latent heats of evaporation and
fusion. Therefore, considerable energy is required to cause phase
changes, the energy being utilised in hydrogen-bond rupturing. More-
over, it has a high specific heat and is a good conductor of heat.
Consequently, heat transfer in water by advection and conduction gives
rise to uniform temperatures. The density of pure water exhibits anom-
alous behaviour. In ice, O atoms have 4 H atoms orientated about them
in a tetrahedral configuration. These units are packed together with a
hexagonal symmetry. At the freezing point, 0 1C, ice is less dense than
water. Heating breaks some hydrogen bonds and the molecules can
achieve slightly closer packing causing the density to increase. Thus, the
maximum density occurs at 4 1C because thermal expansion at higher
temperatures compensates for this compression effect. As will be dis-
cussed later, seawater differs in this respect. Thus, fresh ice floats on
water, which in part explains how rivers and lakes can freeze over, while
remaining liquid at depth. With respect to other properties, water has a
high surface tension that is manifest in stable droplet formation and has
a relatively low molecular viscosity and therefore is quite a mobile fluid.
Water is an excellent solvent. It is extremely polar and can dissolve a
wider range of solutes and in greater amounts than any other substance.
Water has a very high dielectric constant, a measure of the solvent’s
ability to keep apart oppositely charged ions. The solvating characteristics
of individual ions influence their behaviour in solution, i.e., in terms of
hydration, hydrolysis and precipitation. Although water exhibits amp-
hoteric behaviour, electrolytic dissociation is quite small. Furthermore,
dissociation gives equal ion concentrations of both H
3
O
1
and OH
÷
and
so pure water is neutral. The amphoteric behaviour enhances dissolution
of introduced particulate matter through surface hydrolysis reactions.
While the concept will be considered in detail below, the term salinity
(S%) is introduced here as a measure of the salt content of seawater, a
174 Chapter 4
typical value for oceanic waters being 35 g kg
÷1
. In an oceanographic
context, the most important consequence of the addition of salt to water
is the effect on density. However, many of the characteristics outlined
above are also altered. The addition of electrolytes can cause a small
increase in the surface tension. This effect is not commonly observed in
seawater due to the presence of surfactants, which decrease the surface
tension and so facilitate foam formation. As illustrated in Figure 2, the
presence of salt does depress the temperature of maximum density and
the freezing point of the solution relative to pure water. Thus, seawater
with a typical salt content of 35 g kg
÷1
freezes at approximately ÷1.9 1C
and the resulting ice is denser than the solution. However, more often
than the formation of sea ice itself, the freezing process tends to produce
fresh ice overlying a more concentrated brine solution. Salts can be
precipitated at much lower temperatures, i.e., mirabilite (Na
2
SO
4
.2H
2
O)
at ÷8.2 1C and halite (NaCl) at ÷23 1C. Some brine inclusions and salt
crystals can become incorporated into the ice.
From an oceanographic perspective, the fundamental properties of
seawater are temperature, salinity and pressure (i.e., depth dependent).
Together, these parameters control the density of the water, which in
turn determines the buoyancy of the water and pressure gradients. Small
density differences integrated over oceanic scales cause considerable
pressure gradients and result in currents.
Figure 2 The temperature of maximum density (—) and freezing point (- -) of seawater
as a function of dissolved salt content
(Adapted from Tchernia, 1980.
2
)
175 Chemistry of the Oceans
Surface water temperatures are extremely variable, obviously influ-
enced by location and season. The minimum temperature found in polar
latitudes approaches the freezing point of nearly ÷2 1C. Equatorial
oceanic waters can reach 30 1C. Temperature variations with depth are
far from consistent. In a region where mixing prevails, as observed
especially in the surface waters, a layer forms with a relatively uniform
temperature. The zone immediately beneath normally exhibits a sharp
change in temperature, known as the thermocline. The thermocline in
the ocean extends down to about 1000 m within equatorial and tem-
perate latitudes. It acts as an important boundary in the ocean, sepa-
rating the surface and deep layers and limiting mixing between these two
reservoirs.
Below the thermocline, the temperature changes only little with depth.
The temperature is a non-conservative property of seawater because
adiabatic compression causes a slight increase in the in situ temperature
measured at depth. For instance in the Mindanao Trench in the Pacific
Ocean, the temperature at 8500 and 10,000 m is 2.23 and 2.48 1C,
respectively. The term potential temperature is defined to be the tem-
perature that the water parcel would have if raised adiabatically to the
ocean surface. For the examples above, the potential temperatures are
1.22 and 1.16 1C, respectively. Potential temperature of seawater is a
conservative index.
Salinity in the surface waters in the open ocean range between 33 and
37 (Figure 3), the main control being the balance between evaporation
and precipitation. The highest salinities occur in regional seas, where the
evaporation rate is extremely high, namely the Mediterranean Sea (38–
39) and the Red Sea (40–41). Within the World Ocean, the salinity is
greatest in latitudes of about 201 where the evaporation exceeds precip-
itation. Lower salinities occur poleward as evaporation diminishes and
near the equator where precipitation is very high. Local effects can be
important, as evident in the vicinity of large riverine discharges that
dilute the salinity. Salinity variations with depth are related to the origin
of the deepwaters and so will be considered in the section on oceanic
circulation. A zone in which the salinity exhibits a marked gradient is
known as a halocline.
Whereas the density of pure water is 1.000 g ml
÷1
, the density of
seawater (S% = 35) is about 1.03 g ml
÷1
. The term ‘sigma-tee’, s
t
, is
used to denote the density (actually the specific gravity and hence it is a
dimensionless number) of water at atmospheric pressure based on
temperature and salinity in situ. Density increases, and so the buoyancy
decreases, with an increase in s
t
. It is defined as
s
t
= (specific gravity
S%,T
÷ 1) × 1000
176 Chapter 4
In a plot of temperature against salinity (a T–S diagram), constant s
t
appear as curved lines, which denote waters of constant pressure and are
known as isopycnals. A zone in which the pressure changes greatly is
known as a pycnocline. Within the water column, a pycnocline, there-
fore, separates water with distinctive temperature and salinity charac-
teristics, usually indicative of different origins. A T–S diagram can also
be used to estimate the properties resulting from the mixing of two water
masses. As noted above, the temperature is not a conservative property,
and therefore s
t
is also non-conservative. To circumvent the associated
difficulties of interpretation, an analogous term known as the potential
density, s
y
, is defined on the basis of potential temperature instead of in
situ temperature. The s
y
is therefore a conservative index.
4.1.3 Salinity Concepts
Salinity is a measure of the salt content of seawater. Developments in
analytical chemistry have led to an historical evolution of the salinity
concept. Intrinsically, it would seem to be a relatively straightforward
task to measure. This is true for imprecise determinations that can be
quickly performed using a hand-held refractometer. The salinity affects
seawater density and thus, the impetus for high precision in salinity
measurements came from physical oceanographers.
Figure 3 The distribution of mean annual salinity in the surface waters of the ocean
(Adapted from The Open University, 1989.
3
)
177 Chemistry of the Oceans
The first techniques utilised for the determination of salinity, involving
the gravimetric analysis of salt left after evaporating seawater to dryness,
were fraught with difficulties. Variable amounts of water of crystallisation
might be retained. Some salts, such as MgCl
2
, can decompose leaving
residues of uncertain composition. Other constituents, especially organic
material, might be volatilised or oxidised. Overall, such methods led to
considerable inconsistencies and inaccuracies.
The second set of procedures for salinity measurement made use of the
observation from the Challenger expedition of 1872–1876 that sea-salt
composition was apparently invariant. Hence, the total salt content
could be calculated from any individual constituent, such as Cl
÷
that
could be readily determined by titration with Ag
1
. At the turn of the
century, Knudsen defined salinity to be the weight in grams of dissolved
inorganic matter contained in 1 kg of seawater, after bromides and
iodides were replaced by an equivalent amount of chloride and carbon-
ate was converted to oxide. Clearly from the adopted definition, the
analytical technique was not specific to Cl
÷
and so the term chlorinity
was introduced. Chlorinity (Cl%) is the chloride concentration in sea-
water, expressed as g kg
÷1
, as measured by Ag
1
titration (i.e., ignoring
other halide contributions by assuming Cl
÷
to be the only reactant). The
relationship of interest was that between S% and Cl%, given as
S% = 1.805Cl% ÷ 0.030
As a calibrant solution for the AgNO
3
titrant, Standard Seawater was
prepared that had certified values for both chlorinity and salinity.
Unfortunately, the above salinity–chlorinity relationship was derived
from only nine seawater samples that were somewhat atypical. It has
since been redefined using a much larger set of samples representative of
oceanic waters to become
S% = 1.80655Cl%
The third category of salinity methodologies was based on conductome-
try, as the conductivity of a solution is proportional to the total salt
content. Standard Seawater, now also certified with respect to conduc-
tivity, provides the appropriate calibrant solution. The conductivity of a
sample is measured relative to the standard and converted to salinity in
practical salinity units (psu). Note that although psu has replaced the
outmoded %, usually units are ignored altogether in modern usage. These
techniques continue to be the most widely used methods because con-
ductivity measurements can provide salinity values with a precision of
±0.001 psu. Highly precise determinations require temperature control of
samples and standards to within ±0.001 1C. Application of a non-specific
technique like conductometry relies upon the assumption that the sea-salt
178 Chapter 4
matrix is invariant, both spatially and temporally. Thus, the technique
cannot be reliably employed in marine boundary environments where the
seawater composition differs to the bulk characteristics.
There are two types of conductometric procedures commonly used.
Firstly, a Wheatstone Bridge circuit can be set up, whereby the ratio of
the resistance of unknown seawater to standard seawater balances the
ratio of a fixed resistor to a variable resistor. The system uses alternating
current to minimise electrode fouling. Alternatively, the conductivity
can be measured by magnetic induction, in which case the sensor
consists of a plastic tube containing sample seawater that links two
transformers. An oscillator establishes a current in one transformer that
induces current flow within the tube, the magnitude of which depends
upon the salinity of the sample. This in turn induces a current in the
second transformer, which can then be measured. This design has been
exploited for in situ conductivity measurements.
4.1.4 Oceanic Circulation
The distribution of chemical components within the ocean is determined
by both transportation and transformation processes. A brief outline of
oceanic circulation is necessary to ascertain the relative influences. Two
main flow systems must be considered. Surface circulation is established
by tides and the prevailing wind patterns and deep circulation is deter-
mined by gravitational forces. Both are modified by Coriolis force, the
acceleration due to the earth’s rotation. It acts to deflect moving fluids
(i.e., both air and water) to the right in the northern hemisphere and to
the left in the southern hemisphere. The magnitude of the effect is a
function of latitude, being nil at the equator and increasing poleward.
Surface oceanic circulation is depicted in Figure 4. For the most part,
the circulation patterns describe gyres constrained by the continental
boundaries. The prevailing winds acting under the influence of Coriolis
force result in clockwise and counter-clockwise flow in the northern and
southern hemispheres, respectively. The flow fields are non-uniform,
exhibiting faster currents along the western margins. These are manifest,
for example, as the Gulf Stream, Kuroshio Current and Brazil Current.
Circulation within the Indian Ocean is exceptional in that there are
distinct seasonal variations in accord with the monsoons. The absence of
other continents within the immediate boundary region of Antarctica
gives rise to a circumpolar current within the Southern Ocean.
The surface circulation is restricted to the upper layer influenced by the
wind, typically about 100 m. However, underlying water can be trans-
ported up into this zone when horizontal advection is insufficient to
179 Chemistry of the Oceans
maintain the superimposed flow fields. This process is called upwelling
and is of considerable importance in that biochemical respiration of
organic material at depth ensures that the ascending water is nutrient-
rich. Upwelling occurs notably in the eastern oceanic boundaries where
longshore winds result in the offshore transport of the surface water.
Examples are found off the coasts of Peru and West Africa. Similar
processes cause upwelling in the Arabian Sea, but this is seasonal due to
the monsoon effect. A divergence is a zone in which the flow fields
separate. In such a case, upwelling may result as observed in the equa-
torial Pacific. It should be noted that a region in which the streamlines
come together is known as a convergence, and the water sinks in this zone.
The density of the water controls the deepwater circulation. If the
density of a water body increases, it has a tendency to sink. Subsequently,
it will spread out over a horizon of uniform s
y
. As the density can be
raised due to either an increase in the salinity or a decrease in the
temperature, the deepwater circulatory system is also known as thermoh-
aline circulation. As shown in Figure 5 of the ocean conveyor belt, the
densest oceanic waters are formed in Polar Regions due to the relatively
low temperatures and the salinity increase that results from ice formation.
Antarctic Bottom Water (ABW) is generated in the Weddell Sea and flows
northward into the South Atlantic. North Atlantic Deep Water (NADW)
Figure 4 The surface circulation in the ocean
(Adapted from Stowe, 1979.
4
)
180 Chapter 4
is formed in the Norwegian Sea and off the southern coast of Greenland.
The flow of the NADW can be traced southwards through the Atlantic
Ocean to Antarctica, where it is diverted eastward into the Southern
Indian Ocean and South Pacific. There it heads northwards and either
enters the North Pacific or becomes mixed upward into the surface layer in
the equatorial region. The transit time is on the order of 1000 years. As
noted previously, the thermocline acts as an effective barrier against
mixing of dissolved components in the ocean. Consequently, this deepwa-
ter formation process in high latitudes is important because it facilitates
the relatively rapid transport of material from the surface of the ocean
down to great depths. The deep advection of atmospherically derived CO
2
is a pertinent example. The formation of NADW could diminish with
climate change because surface waters would be warmer and less dense due
to enhanced melting of ice in the Arctic region.
Diverse processes can form intermediate waters within the water
column. In the southern South Atlantic, the NADW overrides the
denser ABW. Antarctic Intermediate Water results from water sinking
along the Antarctic Convergence (B501S). Relatively warm, saline
Figure 5 A schematic diagram of the thermohaline circulation of the world ocean, also
know as the great ocean conveyor belt, highlighting polar regions of deepwater
formation, deepwater circulation eastward from the poles and the returning
westward surface water flow
(Adapted from IPCC, 2001.
5
)
181 Chemistry of the Oceans
water exits the Mediterranean Sea at depth and can be identified as a
distinctive layer within the North and South Atlantic.
4.2 SEAWATER COMPOSITION AND CHEMISTRY
4.2.1 Major Constituents
The major constituents in seawater are conventionally taken to be those
elements present in typical oceanic water of salinity 35 that have a
concentration greater than 1 mg kg
÷1
, excluding Si, which is an impor-
tant nutrient in the marine environment. The concentrations and main
species of these elements are presented in Table 1. One of the most
significant observations from the Challenger expedition of 1872–1876
was that these major components existed in constant relative amounts.
As already explained, this feature was exploited for salinity determina-
tions. Inter-element ratios are generally constant, and often expressed as
a ratio to Cl% as shown in Table 1. This implies conservative behaviour,
with concentrations depending solely upon mixing processes, and in-
deed, salinity itself is a conservative index.
Because of this behaviour, individual seawater constituents can be
utilised for source apportionment studies in non-marine environments.
For instance, an enrichment factor (EF) for a substance X is defined as
EF
X
=
X=Na
÷
( )
sample
X=Na
÷
( )
seawater
(4:2)
An EF of 1 indicates that the substance exists in comparable relative
amounts in the sample and in seawater, thereby giving a good indication
Table 1 Chemical species and concentrations of the major elements in seawater
Element Chemical species
Concentration
(mol L
÷1
)
For S = 35
(g kg
÷1
)
Ratio to chlorinity
(Cl = 19.374%)
Na Na
1
4.79 × 10
÷1
10.77 5.56 × 10
÷1
Mg Mg
21
5.44 × 10
÷2
1.29 6.66 × 10
÷2
Ca Ca
21
1.05 × 10
÷2
0.4123 2.13 × 10
÷2
K K
1
1.05 × 10
÷2
0.3991 2.06 × 10
÷2
Sr Sr
21
9.51 × 10
÷5
0.00814 4.20 × 10
÷4
Cl Cl
÷
5.59 × 10
÷1
19.353 9.99 × 10
÷1
S SO
4

, NaSO
4
÷
2.89 × 10
÷2
0.905 4.67 × 10
÷2
C (inorganic) HCO
3
÷
, CO
3

2.35 × 10
÷3
0.276 1.42 × 10
÷2
Br Br
÷
8.62 × 10
÷4
0.673 3.47 × 10
÷3
B B(OH)
3
, B(OH)
4
÷
4.21 × 10
÷4
0.0445 2.30 × 10
÷3
F F
÷
, MgF
1
7.51 × 10
÷5
0.00139 7.17 × 10
÷5
Source: based on Dyrssen and Wedborg, 1974.
6
182 Chapter 4
of a marine origin. If EF
X
4 1, then it is enriched with respect to
seawater. Conversely, depletion is signified when values EF
X
o1. An-
other example of the application of inter-element ratios can be found in
examining the geochemical cycle of sulfur. Concentrations of SO
4

and
Na
1
in ice cores and marine aerosols exhibit a SO
4

/Na
1
greater than
that observed in seawater. This excess can be readily calculated and is
known as non-sea salt sulfate (NSSS). Contributions to NSSS include
SO
2
derived from both volcanic and anthropogenic sources, together
with dimethylsulfide (DMS) of marine biogenic origin.
Not all the major constituents consistently exhibit conservative be-
haviour in the ocean. The most notable departures occur in deepwaters,
where Ca
21
and HCO
3
÷
exhibit anomalously high concentrations due
to the dissolution of calcite. The concept of relative constant composi-
tion does not apply in a number of atypical environments associated
with boundary regions. Inter-element ratios for major constituents can
be quite different in estuaries and near hydrothermal vents. Obviously,
these are not solutions of sea salt with the implication that accuracy
of salinity measurements by chemical and conductometric means is
limited.
The residence times for some elements are presented in Table 2. The
major constituents normally have long residence times. The residence
time is a crude measure of a constituent’s reactivity in the reservoir. The
aqueous behaviour and rank ordering can be appreciated simply in
terms the ionic potential given by the ratio of electronic charge to ionic
radius (Z/r). Elements with Z/ro3 are strongly cationic. The positive
charge density is relatively diffuse, but sufficient to attract an envelope
of water molecules to form a hydrated cation. As the ionic potential
increases, the force of attraction towards the water similarly rises to the
extent that one oxygen – hydrogen bond in the molecule breaks. This
causes the solution pH to fall and metal hydroxides to form. Neutral
hydroxides tend to be relatively insoluble and so precipitate. However,
in the more extreme case for which Z/r 4 12, the attraction towards the
oxygen is so great that both bonds in the associated water molecules are
broken. The reaction product is an oxyanion, usually quite soluble
because of the associated anionic charge. Thus in seawater, those
elements (Al, Fe) having a tendency to form insoluble hydroxides have
short residence times. This is also true for elements that exist preferen-
tially as neutral oxides (Mn, Ti). Hydrated cations (Na
1
, Ca
21
) and
strongly anionic species (Cl
÷
, Br
÷
, UO
2
(CO
3
)
2

) have long residence
times. This treatment is, of course, somewhat of an over-simplification
ignoring the rather significant role that biological organisms play in
nutrient and trace element chemistry.
183 Chemistry of the Oceans
4.2.2 Dissolved Gases
4.2.2.1 Gas Solubility and Air–Sea Exchange Processes. The ocean
contains a vast array of dissolved gases. Some of the gases, such as Ar
and chlorofluorocarbons (CFCs), behave conservatively and can be
utilised as tracers for water mass movements and ventilation rates.
Equilibrium processes at the air–sea interface generally lead to satura-
tion, and the concentration then remains unchanged once the water
sinks. Thus, the gas concentration is characteristic of the lost contact
with the atmosphere. There are several important non-conservative
gases, which exhibit wide variations in concentration due to biological
activity. O
2
determines the redox potential in seawater and CO
2
buffers
Table 2 The residence time and speciation of some elements in the ocean
Element Principal species
Concentration
(mol L
÷1
)
Residence time
(year)
Li Li
1
2.6 × 10
÷5
2.3 × 10
6
B B(OH)
3
, B(OH)
4
÷
4.1 × 10
÷4
1.3 × 10
7
F F
÷
, MgF
1
6.8 × 10
÷5
5.2 × 10
5
Na Na
1
4.68 × 10
÷1
6.8 × 10
7
Mg Mg
21
5.32 × 10
÷2
1.2 × 10
7
Al Al(OH)
4
÷
, Al(OH)
3
7.4 × 10
÷8
1.0 × 10
2
Si Si(OH)
4
7.1 × 10
÷5
1.8 × 10
4
P HPO
4

, PO
4

, MgHPO
4
2 × 10
÷6
1.8 × 10
5
Cl Cl
÷
5.46 × 10
÷1
1 × 10
8
K K
1
1.02 × 10
÷2
7 × 10
6
Ca Ca
21
1.02 × 10
÷2
1 × 10
6
Sc Sc(OH)
3
1.3 × 10
÷11
4 × 10
4
Ti Ti(OH)
4
2 × 10
÷8
1.3 × 10
4
V H
2
VO
4
÷
, HVO
4

, NaHVO
2
÷
5 × 10
÷8
8 × 10
4
Cr CrO
4

, NaCrO
4
÷
5.7 × 10
÷9
6 × 10
3
Mn Mn
21
, MnCl
1
3.6 × 10
÷9
1 × 10
4
Fe Fe(OH)
3
3.5 × 10
÷8
2 × 10
2
Co Co
21
, CoCO
3
, CoCl
1
8 × 10
÷10
3 × 10
4
Ni Ni
21
, NiCO
3
, NiCl
1
2.8 × 10
÷8
9 × 10
4
Cu CuCO
3
, CuOH
1
, Cu
21
8 × 10
÷9
2 × 10
4
Zn ZnOH
1
, Zn
21
, ZnCO
3
7.6 × 10
÷8
2 × 10
4
Br Br
÷
8.4 × 10
÷4
1 × 10
8
Sr Sr
21
9.1 × 10
÷5
4 × 10
6
Ba Ba
21
1.5 × 10
÷7
4 × 10
4
La La
31
, LaCO
3
1
, LaCl
21
2 × 10
÷11
6 × 10
2
Hg HgCl
4

1.5 × 10
÷10
8 × 10
4
Pb PbCO
3
, Pb(CO
3
)
2

, PbCl
1
2 × 10
÷10
4 × 10
2
Th Th(OH)
4
4 × 10
÷11
2 × 10
2
U UO
2
(CO
3
)
2

1.4 × 10
÷8
3 × 10
6
Source: based on Brewer, 1975
7
and Bruland, 1983.
8
184 Chapter 4
the ocean at pH 8. Ocean–atmosphere exchange processes for gases such
as CO
2
and DMS may play an important role in climate change.
Both temperature and salinity affect the solubility of gases in water.
Empirical relationships can be found elsewhere.
9,10
The trends are such
that gas solubility increases with a decrease in temperature or an
increase in salinity. The changes in solubility are non-linear and differ
dramatically for various gases. Whereas Figure 6 depicts the solubility of
several gases as a function of temperature, Figure 7 shows the influence
of both salinity and temperature on the solubility of molecular nitrogen.
At the ocean–atmosphere interface, the exchange of gases occurs to
achieve equilibrium between the two systems, and consequently gases
become saturated in the water. However, supersaturation can be
achieved by several mechanisms. Firstly, bubbles that form from white
cap activity can be entrained and are dissolved at depth. The slight but
significantly greater pressure at depth relative to the surface favours gas
dissolution, and establishes a higher equilibrium concentration. Sec-
ondly as evident from Figure 6, if two water masses that have been
Figure 6 The solubility of various gases in seawater as a function of temperature
(Adapted from Broecker and Peng, 1982.
11
)
185 Chemistry of the Oceans
equilibrated at different temperatures were mixed, then the resulting
water body would be supersaturated. Thirdly, gases like oxygen that are
produced in situ by biological activity may become supersaturated,
particularly when evasion to the atmosphere is hindered.
The gas solubility for a water body in equilibrium with the overlying
air mass can be expressed in several ways. It is convenient to consider
Henry’s Law that states
H = c
a
c
w
÷1
where H is the Henry’s law constant and c
a
and c
w
refer to the
concentration of a gas in air and water, respectively. As discussed by
Liss (1983),
12
air–sea exchange occurs when a concentration gradient
exists (i.e., DC = c
a
H
÷1
÷c
w
) and the magnitude of the consequential
flux, F, is given as
F = K DC
where the proportionality constant, K, has dimensions of velocity and so
is frequently referred to as the transfer velocity. The concept is elabo-
rated upon in Chapter 7.
Air–sea exchange processes are consequently dependent upon the
concentration gradient and the transfer velocity. The transfer velocity
is not a constant, but rather depends upon several physical parameters,
such as temperature, wind speed and wave state. The exchange can also
be attenuated by the presence of a surface film or slick. Alternatively, the
exchange can be facilitated by bubble formation. The concentration
Figure 7 The solubility of nitrogen in seawater as a function of temperature and salinity
186 Chapter 4
gradient determines the direction of the flux, into or out of the ocean.
Net global fluxes for some gases are presented in Table 3. The atmos-
phere serves as the source of material for conservative gases, especially
those of anthropogenic origin, but several gases produced in situ by
biological activity evade from the ocean.
4.2.2.2 Oxygen. Oxygen is a non-conservative gas and a typical
oceanic profile is shown in Figure 8. The concentration varies through-
out the water column, its distribution being greatly influenced by
biological activity. The generalised chemical equation for carbon fixa-
tion is often given as
nCO
2
÷ nH
2
O "(CH
2
O)
n
÷ nO
2
During photosynthesis this reaction proceeds to the right, thereby
producing organic material, as designated by (CH
2
O)
n
, and O
2
. The
surface waters become equilibrated with respect to atmospheric O
2
, but
they can get supersaturated during periods of intense photosynthetic
activity. Respiration occurs as the above reaction proceeds to the left
and O
2
is consumed. Photosynthesis is obviously restricted to the photic
zone in the upper ocean and ordinarily exceeds respiration. However,
the relative importance of the two processes changes with depth. The
oxygen compensation depth is the horizon in the water column at which
the rate of O
2
production by photosynthesis equals the rate of respira-
tory O
2
oxidation.
Below the photic zone, O
2
is utilised in chemical and biochemical
oxidation reactions. As evident in Figure 8, the concentration diminishes
Table 3 The net global fluxes of some trace gases across the air/sea interface
Gas Global air–sea direction
a
Flux magnitude (g yr
÷1
)
CH
4
÷ 10
12
÷10
13
CO
2
÷ 6 × 10
15
N
2
O ÷ 6 × 10
12
{ CCl
4
÷ 10
10
{ CCl
4
= B0
{ CCl
3
F ÷ 5 × 10
9
{ CCl
3
F = B0
CH
3
I ÷ 3–13 × 10
11
CO ÷ 100 ± 90 × 10
12
H
2
÷ 4±2 × 10
12
Hg ÷ B2 × 10
9
a
÷ sea to air; ÷ air to sea;=no net flux.
Source: from Chester, 1990.
1
187 Chemistry of the Oceans
with depth to develop an oxygen minimum zone. Thereafter, the O
2
concentration in deeper waters begins to increase because these waters
originated from Polar Regions. They were cold and in equilibrium with
atmospheric gases at the time of sinking, but subsequently lost little of
the dissolved O
2
because the flux of organic material to deepwaters is
relatively small.
The dissolved O
2
content of seawater has a significant control on the
redox potential, often designated in environmental chemistry by pe (see
also Chapter 3). This is defined with reference to electron activity in an
analogous fashion to pH and thus
pe = ÷ log¦ e
÷
¦
The relationship between pe and the more familiar electrode potential E
or E
H
is
pe =
F
2:303RT
E (4:3)
Figure 8 A profile of molecular oxygen in the North Pacific Ocean
(Data from Bruland, 1980.
13
)
188 Chapter 4
and for the standard state
pe
·
=
F
2:303RT
E
·
(4:4)
where F is Faraday’s constant, R the universal gas constant and T the
absolute temperature in Kelvin. Whereas a high value of pe indicates
oxidising conditions, a low value signifies reducing conditions. Oxygen
plays a role via the reaction
O
2
÷ 4H
÷
÷ 4e
÷
= 2H
2
O
At 20 1C, K = 10
83.1
and so water of pH=8.1 in equilibrium with
atmospheric O
2
(pO
2
= 0.21 atm) has pe = 12.5. This conforms to
surface conditions, but the pe decreases as the O
2
content diminishes
with depth. The oxygen minimum is particularly well developed beneath
the highly productive surface waters of the eastern tropical Pacific
Ocean, where there is a large flux of organic material to depth and
subsequently considerable oxidation. The O
2
becomes sufficiently de-
pleted (i.e., hypoxia) that the resulting low redox conditions causes
NO
3
÷
to be reduced to NO
2
÷
. Aeolian transport of nitrate to Chesa-
peake Bay can lead to low O
2
conditions. Similarly, intermittent hypoxia
develops in parts of the Gulf of Mexico due to the riverine transport of
nutrients derived from agricultural uses in the Mississippi catchment.
When circulation is restricted vertically due to thermal or saline stratifi-
cation and horizontally by topographic boundaries, the water becomes
stagnant and the oxygen may be completely utilised producing anoxic
conditions. Such regions represent atypical marine environments where
reducing conditions prevail. Well-known examples include the Black Sea,
which is permanently anoxic below 200 m, and the Cariaco Trench, a
depression in the Venezuelan continental shelf. Some fjords, such as Saanich
Inlet in western Canada and Dramsfjord of Norway, may be intermittently
anoxic. Periodic flushing of these inlets by dense, oxygenated waters
displaces deep anoxic water to the surface causing massive fish mortality.
O
2
can be used as a tracer to help identify the origin of water masses.
The warm, saline intrusion into the Atlantic Ocean from the Mediter-
ranean Sea is relatively O
2
deficient. Alternatively, the waters down-
welling from Polar Regions have elevated O
2
concentrations.
4.2.2.3 Carbon Dioxide and Alkalinity. Marine chemists sometimes
adopt activity conventions quite different to those traditionally used in
chemistry. It is useful to preface a discussion about the carbon dioxide–
calcium carbonate system in the oceans with a brief outline of pH scales.
189 Chemistry of the Oceans
Although originally introduced in terms of ion concentration, today the
definition of pH is based on hydrogen ion activity and is
pH = ÷loga
H
where a
H
refers to the relative hydrogen ion activity (i.e., dimensionless,
as is pH). Defined using concentration scales, the pH can be
pH = ÷log c
H
g
H
=c
·

or
pH = ÷log m
H
g
H

m
·
À Á
where c
H
and m
H
represent molar and molal concentrations, c1 and m1 are
the respective standard state conditions (1 mol L
÷1
and 1 mol kg
÷1
), and
g
H
is the appropriate activity coefficient. Obviously g
H
differs in these two
expressions because c1 am1. However, different activity scales may also
be used. In the infinite dilution activity scale, g
H
= 1 as the concentration
of hydrogen ions and all other ions approach 0. For analyses, pH meters
are calibrated using dilute buffers prepared in pure water. Alternatively, in
the constant ionic medium activity scale, g
H
= 1 as the concentration of
hydrogen ions approaches 0, while all other components are maintained
at some constant level. Calibrant buffers are prepared in solutions of
constant ionic composition, and in marine chemistry, this is often a
solution of synthetic seawater. While these two methodologies are equally
justifiable from a thermodynamic point of view, it is important to
appreciate that pH scales so defined are quite different. As a further
consequence, the absolute values for dissociation constants also differ.
The biogeochemical cycle of inorganic carbon in the ocean is ex-
tremely complicated. It involves the transfer of gaseous carbon dioxide
from the atmosphere into solution. Not only is this a reactive gas that
readily undergoes hydration in the ocean, but also it is fixed as organic
material by marine phytoplankton. Inorganic carbon can be regenerated
either by photochemical oxidation in the photic zone or via respiratory
oxidation of organic material at depth. Surface waters are supersatu-
rated with respect to aragonite and calcite, different solid phases of
CaCO
3
, but precipitation is limited to coastal lagoons such as found in
the Bahamas. However, several marine organisms utilise calcium car-
bonate to form shells. Sinking shells can remove inorganic carbon from
surface waters that is then regenerated following dissolution in the
under-saturated waters found at depth. Nonetheless, calcitic oozes of
biogenic origin constitute a major component in marine sediments.
190 Chapter 4
Finally, the inorganic carbon equilibrium is responsible for buffering
seawater at a pH near 8 on timescales of centuries to millennia.
There are several equilibria to be considered (see also Chapter 3).
Firstly, CO
2
is exchanged across the air–sea interface
CO
2g
= CO
2aq
The equilibrium process obeys Henry’s Law, but the dissolved CO
2
reacts rapidly with water to become hydrated as
CO
2aq
÷ H
2
O = H
2
CO
3
Relative to the exchange process, the hydration reaction forming carbonic
acid occurs quite quickly. This means that the concentration of dissolved
CO
2
is extremely low. The two processes can be considered together as
CO
2g
÷ H
2
O = H
2
CO
3
The equilibrium constant is then
K
CO
2
=
H
2
CO
3
¦ ¦
p
CO
2
H
2
O ¦ ¦
(4:5)
where p
CO
2
is the partial pressure of CO
2
in the marine troposphere.
Carbonic acid undergoes dissociation
H
2
CO
3
÷ H
2
O = H
3
O
÷
÷ HCO
÷
3
HCO
÷
3
÷ H
2
O = H
3
O
÷
÷ HCO

3
for which the first and second dissociation constants (using {H
1
} rather
than {H
3
O
1
}) are
K
1
=
H
÷
¦ ¦ HCO
÷
3
È É
H
2
CO
3
¦ ¦
(4:6)
K
2
=
H
÷
¦ ¦ CO
2
÷
3
È É
HCO
÷
3
È É
(4:7)
The hydrogen ion activity can be established with a pH meter.
However, as discussed above, this measurement must be operationally
defined. On the other hand, the individual ion activities of bicarbonate
and carbonate ions cannot be measured. Instead, ion concentrations are
determined, as outlined below, by titration. Accordingly, the equilib-
rium constants are redefined in terms of concentrations. These are then
known as apparent, rather than true, equilibrium constants and
191 Chemistry of the Oceans
distinguished using a prime notation. It must be appreciated that
apparent equilibrium constants are not invariant, but rather are affected
by temperature, pressure, salinity, and, as outlined previously, the pH
scale adopted. The apparent dissociation constants are
K
/
1
=
H
÷
¦ ¦ HCO
÷
3
 Ã
H
2
CO
3
[ [
(4:8)
K
/
2
=
H
÷
¦ ¦ CO
2
÷
3
 Ã
HCO
÷
3
 Ã
(4:9)
It should be noted that whereas ion activities are denoted by curly
brackets {}, concentrations are designated by square brackets []. Anal-
ogous to the pH, pK conventionally refers to ÷logK. Numerical values
for the constants pK
CO
2
, pK
/
1
and, pK
/
2
based on a constant ionic
medium scale (i.e., seawater with chlorinity=19%) are given in Table 4.
This provides sufficient information to calculate the speciation of car-
bonic acid in seawater at a given temperature as a function of pH. This is
shown for carbonic acid at 20 1C in both pure water and seawater
equilibrated with atmospheric carbon dioxide in Figure 9. While there
are several confounding features, the pH of seawater can be considered
to be buffered by the bicarbonate/carbonate pair. The pH is generally
about 8, but is sensitive to the concentration ratio [HCO
3
÷
]:[CO
3

] as
evident from rearranging the expression for K
/
2
to become
H
÷
¦ ¦ =K
/
2
HCO
÷
3
 Ã
CO
2
÷
3
 à (4:10)
To understand the response of the oceanic CO
2
system to in situ
biological activity or enhanced CO
2
concentrations in the atmosphere,
Table 4 Equilibrium constants for the carbonate system
T ( 1C) pK
CO
2 pK
/
1
pK
/
2
0 1.19 6.15 9.40
5 1.27 6.11 9.34
10 1.34 6.08 9.28
15 1.41 6.05 9.23
20 1.47 6.02 9.17
25 1.53 6.00 9.10
30 1.58 5.98 9.02
Source: adapted from Stumm and Morgan, 1996.
14
192 Chapter 4
it is necessary to consider in more detail the factors influencing the
inorganic carbon cycle. Two useful parameters can be introduced. Firstly,
the total concentration of inorganic carbon,
P
CO
2
, in seawater is
P
CO
2
= [CO
2
] ÷ [H
2
CO
3
] ÷ [HCO
3
÷
] ÷ [CO
3

]
The first term is negligible and as evident in Figure 9, the major species
at pH 8 are HCO
3
÷
and CO
3

.
Alkalinity is defined as a measure of the proton deficit in solution and
should not to be confused with basicity. Alkalinity is operationally
defined by titration with a strong acid to the carbonic acid end point.
This is known as the titration alkalinity (TA). Seawater contains weak
acids other than bicarbonate and carbonate that are titrated, and
therefore TA is given as
TA = [HCO
3
÷
] ÷ 2[CO
3

] ÷ [B(OH)
4
÷
] ÷ [OH
÷
] ÷ [H
1
]
This is a simplified version of the more general expression in Chapter 3. The
influence of [OH
÷
] and [H
1
] on the TA is small and can often be ignored.
The borate contributes about 3% of the TA, and if not determined
independently, can be estimated from the apparent boric acid dissociation
constants and the salinity, relying upon the relative constancy of compo-
sition of sea salt. This correction would give the carbonate alkalinity (CA)
CA = [HCO
3
÷
] ÷ 2[CO
3

]
Considering the dissociation constants above, this can be alternatively
expressed as
CA =
K
/
1
H
2
CO
3
[ [
H
÷
¦ ¦
÷
2 K
/
1
K
/
2
H
2
CO
3
[ [
H
÷
¦ ¦
2
(4:11)
Figure 9 The distribution of carbonic acid species at 20 1C as a function of pH in seawater
of salinity 35(solid lines) and pure water (dotted lines)
193 Chemistry of the Oceans
or
CA =
K
/
1
K
CO
2
pCO
2
H
÷
¦ ¦
÷
2 K
/
1
K
/
2
K
CO
2
pCO
2
H
÷
¦ ¦
2
(4:12)
This equation can be rearranged to give the following quadratic
expression that can be solved for the pH
CA H
÷
¦ ¦
2
÷K
/
1
K
CO
2
pCO
2
H
÷
¦ ¦ ÷ 2 K
/
1
K
/
2
K
CO
2
pCO
2
= 0
Worked Example 1
For seawater (35 psu, 15 1C) with an alkalinity of 2.30 meq l
÷1
and in
equilibrium with atmospheric CO
2
= 3.65 × 10
÷4
atm, calculate (i)
the pH and (ii) the speciation of carbonic acid.
(i) pH calculation
Data, including constants from Table 4 are K
CO2
= 10
÷1.41
, K
/
1
=
10
÷6.05
, K
/
2
= 10
÷9.23
, CA=2.30 × 10
÷3
, pCO
2
=3.65 × 10
÷4
The pH is obtained from the calculation of {H
1
} using the above
quadratic equation. Thus
H
÷
¦ ¦ =
÷b ÷
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
b
2
÷ 4ac

2a
where
a =CA
=2:30 × 10
÷3
b = ÷ K
/
1
K
CO2
pCO
2
= ÷ 10
÷6:5
10
÷1:41
10
÷3:46
= ÷ 1:20 × 10
÷11
c = ÷ 2 K
/
1
K
/
2
K
CO2
pCO
2
= ÷ 210
÷6:05
10
÷9:23
10
÷1:41
10
÷3:46
= ÷ 1:42 × 10
÷20
Giving {H
1
}=6.22 × 10
÷9
and pH=8.21.
(ii) Carbonic acid speciation calculations
Knowing the pH, each of the three major species (H
2
CO
3
, HCO
3
÷
,
CO
3

) can be calculated as a fraction (or percentage) of the
P
CO
2
.
194 Chapter 4
Note that the negligible contribution due to dissolved CO
2
is ignored.
The necessary expressions are derived from the definitions of the K
/
1
and K
/
2
given previously.
HCO
÷
3
 Ã
K
/
1
H
÷
¦ ¦
H
2
CO
3
[ [ (4:13)
CO

3
 Ã
=
K
/
2
H
÷
¦ ¦
HCO
÷
3
 Ã
=
K
/
1
K
/
2
H
÷
¦ ¦
2
H
2
CO
3
[ [
Substituting into the expression for the summation of all carbonic
species gives
P
CO
2
= [H
2
CO
3
] ÷ [HCO
3
÷
] ÷ [CO
3

]= [H
2
CO
3
] ÷
K
/
1
{H
1
}
÷1
[H
2
CO
3
]÷K
/
1
K
/
2
{H
1
}
÷2
[H
2
CO
3
]= [H
2
CO
3
](1÷
K
/
1
{H
1
}
÷1
÷K
/
1
K
/
2
{H
1
}
÷2
)
Thereafter, the fractional contribution of each species to the total can
be calculated using
1:
[H
2
CO
3
[
P
[CO2[
=
(1 ÷ K
/
1
¦ H
÷
¦
÷1
÷ K
/
1
K
/
2
¦ H
÷
¦
÷2
)
÷1
2:
HCO
÷
3
[ [
P
CO
2
[ [
= K
/
1
H
÷
¦ ¦
À Á
1 ÷ K
/
1
H
÷
¦ ¦
÷1
÷K
/
1
K
/
2
H
÷
¦ ¦
÷2

÷1
3:
[CO

3
[
P
[CO2[
= (K
/
1
K
/
2
¦ H
÷
¦
÷2
)
(1 ÷ K
/
1
¦ H
÷
¦
÷1
÷ K
/
1
K
/
2
¦ H
÷
¦
÷2
)
÷1
Substituting the values for K
/
1
and K
/
2
and using the previously
calculated pH of 8.21, the fractional contribution of each species is
0.006, 0.907 and 0.087 for H
2
CO
3
, HCO
3
÷
, and CO
3

, respectively.
Consider now the effect of altering the pCO
2
in the water. The
alkalinity should not change in response to variations in CO
2
alone
because the hydration and dissociation reactions give rise to equivalent
amounts of H
1
and anions. CO
2
can be lost by evasion to the atmos-
phere (a process usually confined to equatorial regions) or by photo-
synthesis. This causes the
P
CO
2
to diminish and the pH to rise, an
effect that can be quite dramatic in tidal rock pools in which pH may
then rise to 9. Conversely, an increase in pCO
2
, either by invasion from
the atmosphere or release following respiration, prompts an increase in
195 Chemistry of the Oceans
P
CO
2
and a fall in pH. Thus, the depth profiles of pH would mimic that
of O
2
but the
P
CO
2
would exhibit a maximum at the oxygen minimum.
There are further confounding influences, in particular concerning the
solid phases of CaCO
3(s)
. Many organisms make calcareous shells
(testes) of CaCO
3(s)
in the form of either aragonite or calcite. The shells
sink and dissolve when the organism dies. The solubility is governed by
Ca

÷ CO

3
= CaCO
3(s)
Surface waters are supersaturated with respect to CaCO
3(s)
, but precip-
itation rarely occurs, possibly due to an inhibitory effect by Mg
21
aq
forming ion pairs with CO
3

aq
. The solubility of CaCO
3(s)
increases
with depth, due to both a pressure effect and the decrease in pH
following respiratory release of CO
2
, causing the shells to dissolve. This
behaviour not only increases the alkalinity, but also accounts for the
non-conservative nature of Ca
21
and inorganic carbon in deepwaters.
The depth at which appreciable dissolution begins is known as the
lysocline. At a greater depth, designated as the carbonate compensation
depth (CCD), no calcareous material is preserved in the sediments. The
depths of the lysocline and CCD are influenced by the flux of organic
material and shells, and tend to be deeper under high productivity zones.
The CO
2
and CaCO
3(s)
systems are coupled in that the pH buffering in
the ocean is due to the reaction
CO
2
÷ H
2
O ÷ CaCO
3(s)
= Ca

÷ 2HCO
÷
3
In addition to the effects noted previously, an input of CO
2
promotes the
dissolution of CaCO
3(s)
. The reaction does not proceed to the right
without constraint, but rather meets a resistance given by the Revelle
factor, R
R =
dpCO
2
=pCO
2
d
P
CO
2
=
P
CO
2
(4:14)
This value is approximately 10, indicating that the ocean is relatively
well buffered against changes in
P
CO
2
in response to variations in
atmospheric pCO
2
. Although the ocean does respond to an increase in
the atmospheric burden of CO
2
, the timescales involved are quite
considerable. The surface layer can become equilibrated on the order
of decades, but as the thermocline inhibits exchange into deepwaters, the
equilibration of the ocean as a whole with the atmosphere proceeds on
the order of centuries. The ventilation of deepwater by downwelling
196 Chapter 4
water masses in polar latitudes only partly accelerates the overall
process.
4.2.2.4 Dimethylsulfide and Climatic Implications. The Gaia hypoth-
esis of Lovelock
15
states that the biosphere regulates the global envi-
ronment for self-interest. This pre-supposes that controls, perhaps
poorly understood or unknown, serve to maintain the present status
quo. Charlson et al.
16
have made use of this hypothesis to suggest that
biogenic production of DMS and the consequent formation of atmos-
pheric cloud condensation nuclei (CCN, i.e., small particles onto which
water can condense) acts as a feedback mechanism to counteract the
global warming resulting from elevated greenhouse gas concentrations
in the atmosphere. The cycle is illustrated in Figure 10. Global warming,
with concurrent warming of the ocean surface, leads to enhanced
phytoplankton productivity. This promotes the production and evasion
to the atmosphere of DMS. The DMS undergoes oxidation to form
CCN that promote cloud formation and increase the planetary albedo
(i.e., reflectivity with respect to sunlight) thereby causing a cooling
effect. From a biogeochemical perspective, the two key features are
the controls on the biogenic production of DMS and the formation of
CCN following aerial oxidation of DMS. These will be considered below
in more detail. With respect to the physics, the most important aspects
of the proposed climate control mechanism are that the enhancement of
the albedo is due to an increase in the number and type of CCN, and that
this CCN production occurs in the marine boundary layer. The albedo
of calm seawater is very low (B2%) in comparison to vegetated regions
(10–25%), deserts (B35%), and snow-covered surfaces (B90%).
That biological processes within the oceans act as a major source of
reduced sulfur gases is well established,
17
and of particular importance is
the generation of DMS. Surface concentrations, approximately in the
range of 0.7–17.8 nmol L
÷1
, exhibit large temporal and geographic
variations. Oceanic distributions indicate that DMS is produced within
the photic zone, that is consistent with a phytoplankton source, but
DMS concentrations are poorly correlated with normal indicators of
primary productivity. While Phaeocystis and Coccolithoporidae have
been identified as important DMS producers, there is uncertainty as to
the full potential for biological DMS formation. With respect to climate
modification, questions remain as to the biological response to global
warming. For the model of Charlson et al.
16
to hold, organisms might
either increase DMS formation or biological succession could change in
such a way as to favour DMS producers. Thus, marine biogenic source
197 Chemistry of the Oceans
strengths and the controlling factors remain important unresolved issues
in sulfur biogeochemistry.
DMS concentrations in the remote marine troposphere vary in the
range of 0.03–32 nmol m
÷3
. Not surprisingly and as with the seawater
concentrations, considerable temporal and geographic disparities occur.
Furthermore, atmospheric DMS concentrations exhibit diurnal varia-
tions, with a night time maximum and an afternoon minimum consistent
with a photochemical sink. Whereas oxidation involves HO free radicals
Figure 10 The possible climatic influence of DMS of marine biogenic origin
(Adapted from Charlson et al., 1987.
16
)
198 Chapter 4
during the day, a reaction with NO
3
may be important at night.
Relatively low levels are associated with air masses derived from con-
tinental areas, owing to the enhanced concentrations of oxidants. While
oceanic venting rates are dependent upon a number of meteorological
and oceanographic conditions, there is no question that the marine
photic zone acts as the major source of DMS to the overlying tropo-
sphere.
The oxidation of DMS in the atmosphere (see also Chapter 2) could
yield several products, namely dimethylsulfoxide (DMSO), methane-
sulfonate (MSA) or sulfate. Insofar as aerosol formation is concerned,
the two key products are MSA and SO
4

. Atmospheric particles in the
sub-micron size range exert a significant influence on the earth’s climate.
The effect can be manifested via three mechanisms. Firstly, the particles
themselves may enhance backscatter of solar radiation. Secondly, they
act as CCN promoting cloud formation and so increasing the earth’s
albedo. Thirdly, such clouds affect the hydrological cycle. The evidence
for such a biofeedback mechanism limiting global warming remains
circumstantial.
4.2.3 Nutrients
Although several elements are necessary to sustain life, traditionally in
oceanography the term ‘‘nutrients’’ has referred to nitrogen (notably,
but not exclusively, nitrate), phosphorus (usually as phosphate), and
silicon (as silicate). The rationale for this classification was that analyt-
ical techniques had long been available that allowed the precise deter-
mination of these constituents despite their relatively low
concentrations. They were observed to behave in a consistent and
explicable manner, but quite differently to the major constituents in
seawater.
The distributions of these three nutrients are determined by biological
activity. Nitrate and phosphate become incorporated into the soft parts
of organisms. As evident in the modified carbon fixation equation of
Redfield
18
given below
106CO
2
÷ 16NO
÷
3
÷ HPO

4
÷ 122H
2
O
÷ 18H
÷
= C
106
H
263
O
110
N
16
P ÷ 138O
2
The uptake of these nutrients into tissues occurs in constant relative
amounts. The ratio (i.e., Redfield ratio) for C/N/P is 106:16:1. Silicate is
utilised by some organisms, particularly diatoms (phytoplankton) and
radiolaria (zooplankton), to form siliceous skeletons. Such skeletons
199 Chemistry of the Oceans
consist of an amorphous, hydrated silicate, SiO
2
nH
2
O, often called
opaline silica.
Photosynthetic carbon fixation depends on the availability of the
nutrients, and of course, it ceases when one of the nutrient supplies is
exhausted. The limiting nutrient in the ocean is usually nitrogen, but
there are conditions under which Fe may limit biological productivity.
Biological productivity is greatest in regions with the greatest supply of
nutrients, such as coastal regions and near zones of upwelling. Moreo-
ver, biological activity is seasonal at most latitudes, being influenced by
PAR coupled with the depletion of nutrients from surface waters that
become thermally stratified due to summer warming.
The biogeochemical cycling of nitrogen in the marine environment is
quite complex, largely owing to the diversity of forms in which it is
present, coupled with the ease with which organisms can either assim-
ilate or transform the various nitrogenous species. Nitrogen exhibits the
range of oxidation states, from N(V) in nitrate to N(÷III) in NH
3
and
numerous organic compounds. Also, N occurs as dissolved gaseous
molecules, including N
2
and N
2
O; dissolved inorganic nitrogen (DIN)
such as NO
3
÷
and NO
2
÷
; dissolved organic nitrogen (DON) present in
organic compounds like amino acids; and particulate organic nitrogen
(PON) in organisms and detritus. Few marine organisms are capable of
assimilating N
2
directly, (known as nitrogen fixation) despite its relative
abundance in seawater. The nitrogenous species more commonly used
are nitrate, nitrite, urea and ammonium.
Bacteria play an important role in the redox chemistry of nitrogen
species in seawater. Starting with PON, the first step is remineralisation
in which PON is converted to DON. The breakdown of some of the
DON to DIN follows with the first product being NH
3
; the process is
relatively rapid and known as ammonification. NH
3
is protonated to a
limited extent in seawater, giving rise to NH
4
1
ions. Nitrification is the
stepwise oxidation of NH
4
1
to NO
2
÷
and eventually to NO
3
÷
. Denitri-
fication, the reduction of nitrogen species to N
2
, can occur under
conditions of hypoxia or anoxia. In such cases, bacteria respire organic
material using NO
3
÷
and NO
2
÷
as electron acceptors.
A depth profile of nitrate, phosphate and silicate in the North Pacific
Ocean is presented in Figure 11. Nutrients behave much like
P
CO
2
and
are removed in the surface layer, especially in the photic zone. Thus,
concentrations can become quite low, and indeed sufficiently low to limit
further photosynthetic carbon fixation. The organisms sink following
death. The highest concentrations occur where respiration and bacterial
decomposition of the falling organic material are greatest, that is at the
oxygen minimum. The nutrients, including silica, are consequently
200 Chapter 4
regenerated and their concentrations in deepwaters are much greater than
those observed in the surface waters, thereby accounting for the fertilising
effect of upwelling. It should be noted that the siliceous remains behave
differently than the calcareous shells discussed previously. The oceans
everywhere are under-saturated with respect to silica. Its solubility exhib-
its no pronounced variation with depth and there is no horizon analogous
to the CCD (see Section 4.2.2.3). Silica is preserved to any great extent
only in deep-sea sediments associated with the highly productive upwell-
ing zones in the ocean.
4.2.4 Trace Elements
Trace elements in seawater are taken to be those that are present in
quantities less than 1 mg L
÷1
, excluding the nutrient constituents. The
distribution and behaviour of minor elements have been reviewed in the
light of data that conform to an oceanographically consistent manner.
1,8
Figure 11 The depth distribution of nitrate (K), phosphate (’), and silicate (m) in the
North Pacific Ocean
(Data from Bruland, 1980.
13
)
201 Chemistry of the Oceans
Analytical difficulties are readily comprehensible when it is appreciated
that the concentration for some of these elements can be extremely low,
i.e., a few pg L
÷1
for platinum group metals.
19
Some trace elements, such
as Cs
1
, behave conservatively and therefore absolute concentrations
depend upon salinity. More often, the elements are non-conservative
and their distributions in both surface waters and the water column vary
greatly, reflecting the differing source strengths and removal processes in
operation. Generalisations regarding residence times cannot be made in
many cases because biologically active elements are removed from seawa-
ter relatively rapidly. Nevertheless, conservative constituents and platinum
group metals have rather long residence times on the order of 10
5
years.
Considering firstly the distribution in surface waters, several elements
exhibit high concentrations in coastal waters in comparison to levels in
the centres of oceanic gyres. Typically, this distribution arises because
the elements originate predominantly from riverine inputs or through
diffusion from coastal sediments. However, as they are effectively
removed from the surface waters in the coastal regions, little material
is advected horizontally to the open sea. Examples of elements that
behave in this way are Cd, Cu and Ni. In contrast, the concentration of
Pb, including
210
Pb, is greater in the gyres. This results from a strong
widespread aeolian input coupled with less effective removal from
surface waters in the gyres.
Clearly, the removal mechanisms have an appreciable effect on dis-
solved elemental abundances. The two major processes in operation are
uptake by biota and scavenging by suspended particulate material. In the
first instance, the constituent mimics the behaviour of nutrients. This is
evident in the metal/nutrient correlation for Cd/P and Zn/Si (Figure 12).
No consistent pattern for depth profiles of trace elements exists.
Conservative elements trend with salinity variations provided they have
no significant submarine sources. Non-conservative elements may ex-
hibit peak concentrations at different depths in oxygenated waters as
(i) surface enrichment,
(ii) maximum at the O
2
minimum,
(iii) mid-depth maximum not associated with the O
2
minimum, and
(iv) bottom enrichment.
The criteria for an element, such as Pb, to exhibit a maximum concen-
tration in surface waters are that the only significant input must be at the
surface (aeolian supply) and it must be effectively removed from the
water column. Constituents such as As, Ba, Cd, Ni and Zn exhibit
nutrient type behaviour. Those elements (Cd) associated with the soft
parts of the organism are strongly correlated with phosphate and are
202 Chapter 4
Figure 12 Metal/nutrient correlations in the North Pacific for Cd/P and Zn/Si
(Adapted from Bruland, 1980.
13
)
203 Chemistry of the Oceans
regenerated at the O
2
minimum. Elements (i.e., Zn) associated with the
skeletal material may exhibit a smoothly increasing trend with depth.
The third case pertains to elements, notably Mn, that have a substantial
input from hydrothermal waters. These are released into oceanic waters
from spreading ridges. Ocean topography is such once these waters are
advected away from such regions towards the abyssal plains, they are
then found at some intermediate depth. Bottom enrichment is observed
for elements (Mn) that are remobilised from marine sediments. The
behaviour of Al combine features outlined above, resulting in a mid-
depth minimum concentration. Surface enrichment evident in mid (411
N) but not high (B601 N) latitudes in the North Atlantic results from
the solubilisation of aeolian material. Removal occurs via scavenging
and incorporation into siliceous skeletal material. Subsequent regener-
ation by shell dissolution increases deepwater Al levels.
4.2.5 Physico-Chemical Speciation
Physico-chemical speciation refers to the various physical and chemical
forms in which an element may exist in the system. In oceanic waters, it
is difficult to determine chemical species directly. Whereas some indi-
vidual species can be analysed, others can only be inferred from ther-
modynamic equilibrium models as exemplified by the speciation of
carbonic acid in Figure 9. Often an element is fractionated into various
forms that behave similarly under a given physical (e.g., filtration) or
chemical (e.g., ion exchange) operation. The resulting partition of the
element is highly dependent upon the procedure utilised, and so known
as operationally defined. In the following discussion, speciation will be
exemplified with respect to size distribution, complexation characteris-
tics, redox behaviour and methylation reactions.
Physico-chemical speciation determines the environmental mobility of
an element, especially with respect to partitioning between the water and
sediment reservoirs. The influence can be manifested through various
mechanisms as summarised in Figure 13. Settling velocities, and by
implication the residence time, are controlled by the size of the particle.
Thus, dissolved to particulate interactions involving adsorption, precip-
itation or biological uptake can readily remove a constituent from the
water column. The redox state can have a comparable influence. Mn and
Fe are reductively remobilised in sediments. Following their release in
reduced forms from either hydrothermal sources or interstitial waters,
they rapidly undergo oxidation to form colloids, which then are quickly
removed from the water column. Speciation also determines the bio-
availability of an element for marine organisms. It is generally accepted
204 Chapter 4
that the uptake of trace elements is limited to free ions and some types of
lipid–soluble organic complexes. This is important in that some elements
may be essential, but toxic at elevated concentrations. Via complexation
reactions, organisms may be able to modify the free ion concentration.
Thus, siderophores can sequester Fe, often in limited supply. Alterna-
tively, metallothionein detoxify contaminants, notably Cd and Hg,
through chelation.
An element can exist in natural waters in a range of forms that exhibit
a size distribution as indicated in Table 5. Entities in true solution
include ions, ion pairs, complexes and a wide range of organic molecules
that can span several size categories. At the smallest extreme are ions,
which exist in solution with a co-ordinated sphere of water molecules as
discussed previously. Na
1
, K
1
and Cl
÷
exist predominantly as free
hydrated ions. Collisions of oppositely charged ions occur due to
electrostatic attraction and can produce an ion pair. An ion pair is the
transient coupling of a cation and anion during which each retains its
own co-ordinated water envelope. While impossible to measure directly,
concentrations can be calculated with knowledge of the ion activities
and the stability constant. For the formation of the ion pair NaSO
4
÷
via
Na
÷
÷ SO
2
4
÷ = NaSO
÷
4
Figure 13 Speciation of metal ions in seawater and the main controlling mechanisms
(Adapted from O
¨
hman and Sjo¨ berg, 1988.
20
)
205 Chemistry of the Oceans
the stability constant is defined as
K =
¦NaSO
÷
4
¦
¦Na
÷
¦¦SO
2
÷
4
¦
(4:15)
Ion pair formation is important for Ca
21
, Mg
21
, SO
4

and HCO
3
÷
.
If the attraction is sufficiently great, a dehydration reaction can occur
leading to covalent bonding. A complex consists of a central metal ion
sharing a pair of electrons donated by another constituent, termed a
ligand, acting as a Lewis base. The metal ion and ligand share a single
water envelope. Ligands can be neutral (e.g., H
2
O) or anionic (e.g., Cl
÷
,
HCO
3
÷
) species. A metal ion can co-ordinate with one or more ligands,
which need not be the same chemical entity. Alternatively, the cation can
share more than one electron pair with a given ligand thereby forming a
ring structure. This type of complex, known as a chelate, exhibits
enhanced stability largely due to the entropy effect of releasing large
numbers of molecules from the co-ordinated water envelopes.
Complex formation is an equilibrium process. Ignoring charges for the
general case of a metal, M and ligand, L, complex formation occurs as
M ÷ L "ML
for which the formation constant, K
1
, is given by
K
1
=
¦ML¦
¦M¦¦L¦
(4:16)
Table 5 The size distribution of trace metal species in natural waters
Size range Metal species Examples Phase state
o 1 nm Free metal ions Mc
21
, Cd
21
Soluble
1–10 nm Inorganic ion pairs NiCl
1
Soluble
Inorganic complexes HgCl
2
4
÷
Low molecular mass organic
complexes
Zn-fulvates
10–100 nm High molecular mass organic
complexes
Pb-humates Colloidal
100–1000
nm
Metal species adsorbed onto
inorganic colloids
Co–MnO
2
Particulate
Metals associated with detritus Pb–Fe(OH)
3
4 1000 nm Metals absorbed into living
cells
Cu–clays Particulate
Metals adsorbed onto or
incorporated into mineral
solids and precipitates
PbCO
3(s)
Source: adapted from de Mora and Harrison, 1984.
21
206 Chapter 4
A second ligand may then be co-ordinated as
M ÷ L "ML
2
K
2
=
¦ML
2
¦
¦ML¦¦L¦
(4:17)
The equilibrium constant for ML
2
can be expressed solely in terms of
the activities of the M and L
b
2
=
¦ML
2
¦
¦M¦¦L¦
2
(4:18)
where ß
2
is the product of K
1
K
2
and is known as the stability constant.
The case can be extended to include n ligands as
b
n
=
¦ML
n
¦
¦M¦¦L¦
n
(4:19)
Worked Example 2
Assuming all g
/
s = 1, calculate the speciation of mercury in typical
seawater (35 psu at 25 1C) given the following values for stepwise
stability constants for successive chlorocomplexes (K
1
= 10
6.74
, K
2
=
10
6.48
, K
3
= 10
0.85
, K
4
= 10
1.00
). Note that [Cl
÷
] is 0.559 mmol L
÷1
and
that it is not necessary to know the mercury concentration in seawater.
The total mercury concentration is given as the sum of all contribut-
ing species. Thus
[Hg]
T
= [Hg
2 1
] ÷ [HgCl
1
] ÷ [HgCl
2
]÷[HgCl
3
÷
] ÷ [HgCl
4

]
From the definition of the stability constants, we know that
[HgCl
1
] = K
1
[Hg
21
][Cl
÷
] and [HgCl
2
] = b
2
[Hg
21
][Cl
÷
]
2
, etc. Thus,
[Hg]
T
=[Hg
21
](1÷K
1
[Cl
÷
]÷b
2
[Cl
÷
]
2
÷b
3
[Cl
÷
]
3
÷b
4
[Cl
÷
]
4
).
Now let D = (1 ÷ K
1
[Cl
÷
] ÷ b
2
[Cl
÷
]
2
÷ b
3
[Cl
÷
]
3
÷ b
4
[Cl
÷
]
4
)
÷1
, and
note that this is a constant for a stipulated chloride concentration.
Thus, at the seawater chloride concentration ([Cl
÷
] = 10
÷0.25
) this gives
D = (1÷10
6.74
10
÷0.25
÷ 10
6.74
10
6.48
10
÷0.25
÷ 10
6.74
0
6.48
10
0.85
10
÷0.25
÷
10
6.74
10
6.48
10
0.85
10
1.00
10
÷0.25
)
÷1
= 7.27 × 10
÷15
The fractional (or percentage) contribution of each species can be
determined using
207 Chemistry of the Oceans
Fractional contribution Expression Value for [Cl
÷
[ = 0:559 mmol L
-1
[Hg

[ : [Hg

[
T
D 7:3 × 10
÷15
[HgCl
÷
[ : [Hg

[
T
D K1[Cl
÷
[ 2:2 × 10
÷8
[HgCl
2
[ : [Hg

[
T
D b
2
[Cl
÷
[
2
3:7 × 10
÷2
(4%)
[HgCl
3
[ : [Hg

[
T
D b
3
[Cl
÷
[
3
1:5 × 10
÷1
(15%)
[HgCl
2-
4
[ : [Hg

[
T
D b
4
[Cl
÷
[
4
8:2 × 10
÷1
(82%)
Thus, at the high chloride concentration found in seawater, the
mercury speciation is dominated by the tetra- and tri-chloro species.
Note (1) If the total mercury content for a given seawater sample were
known, the concentration of each species is readily calculated. That is
[Hg
21
] = f
HG
21
[Hg
21
]T;
(2) This is a simplified example that has not considered other species
(bromides, hydroxides, etc.) that might be important in seawater.
The speciation of constituents in solution can be calculated if the
individual ion activities and stability constants are known. This infor-
mation is relatively well known with respect to the major constituents in
seawater, but not for all trace elements. Some important confounding
variables create considerable difficulties in speciation modelling. Firstly,
it is assumed that equilibrium is achieved, meaning that neither biolog-
ical interference nor kinetic hindrance prevents this state. Secondly,
seawater contains appreciable amounts (at least in relation to the trace
metals) of organic matter. However, the composition of the organic
matrix, the number of available binding sites, and the appropriate
stability constants are poorly known. Nevertheless, speciation models
can include estimates of these parameters. Organic material can form
chelates with relatively high-stability constants and dramatically de-
crease the free ion activity of both necessary and toxic trace elements.
Organisms may make use of such chemistry, producing compounds
either to sequester metals in limited supply (e.g., siderophores to com-
plex Fe) or to detoxify contaminants (e.g., metallothionein to chelate
Cd, Hg, etc.). Thirdly, surface adsorption of dissolved species onto
colloids or suspended particles may remove them from solution. As with
organic matter, an exact understanding of the complexation character-
istics of the suspended particles is not available, but approximations can
also be incorporated into speciation models.
Elements may be present in a variety of phases other than in true
solution. Colloidal formation is particularly important for elements such
as Fe and Mn, which produce amorphous oxyhydroxides with very great
208 Chapter 4
complexation characteristics. Adsorption processes cannot be ignored in
biogeochemical cycling. Particles tend to have a much shorter residence
time in the water column than do dissolved constituents. Scavenging of
trace components by falling particles accelerates deposition to the
sediment sink.
Several elements in seawater may undergo alkylation via either chemical
or biological mechanisms.
22
Type I mechanisms involve methyl radical or
carbonium ion transfer and no formal change in the oxidation state of the
acceptor element. The incoming methyl group may be derived for exam-
ple from methylcobalamin coenzyme, S-adenosylmethionine, betaine or
iodomethane. Elements involved in Type I mechanisms include Pb, Tl, Se
and Hg. Other reaction sequences involve the oxidation of the methylated
element. The methyl source can be a carbanion from methylcobalamin
coenzyme. Oxidative addition from iodomethane and enzymatic reactions
has also been suggested. Some elements that can undergo such methyl-
ation processes are As, Sb, Ge, Sn and S. Methylation can enhance the
toxicity of some elements, especially for Pb and Hg. The environmental
mobility can also be affected. Methylation in the surface waters can
enhance volatility and so favour evasion from the sea, as observed for S,
Se and Hg. Methylation within the sediments may facilitate transfer back
into overlying waters.
Elements may exhibit multiple oxidation states in seawater. Redox
processes can be modelled in an analogous manner to the ion pairing
and complexation outlined previously. The information is often pre-
sented graphically in the form of a predominance area diagram, which is
a plot of pe vs. pH showing the major species present for the designated
conditions. Although a single oxidation state might be anticipated from
equilibrium considerations, there are several ways in which multiple
oxidation states might arise. Biological activity can produce non-equi-
librium species, as evident in the alkylated metals discussed above.
Whereas Mn(IV) and Cu(II) might be expected by thermodynamic
reasoning, photochemical processes in the surface waters can lead to
the formation of significant amounts of Mn(II) and Cu(I). Fe(III) is the
favoured redox state of Fe in seawater, but it is relatively insoluble and
exists predominantly in a colloidal phase. Photochemical reduction to
Fe(II), which only slowly oxidises to Fe(III), might act as a very
important mechanism rendering Fe bioavailable to marine organisms.
Goldberg
19
has presented impressive information (given that seawater
concentrations are as low as 1.5 pg L
÷1
for Ir and 2 pg L
÷1
for Ru) on
the speciation, including redox state, of platinum group metals as a
means of interpreting distributions in seawater and marine sediments. Pt
and Pd are stabilised in seawater as tetrachloro-divalent anions. Their
209 Chemistry of the Oceans
relative abundance of 5 Pt:1 Pd agreeing with a factor of five difference
in ß
4
. Pt is enriched in ferromanganese nodules following oxidation to a
stable (IV) state, behaviour not observed for Pd. Rh exists predomi-
nantly in the heptavalent state, but accumulates in reducing sediments as
lower valence sulfides. Au and Ag are present predominantly in solution
as monovalent forms. Ag, but not Au, accumulates in anoxic coastal
sediments.
4.3 SUSPENDED PARTICLES AND MARINE SEDIMENTS
4.3.1 Description of Sediments and Sedimentary Components
The sediments represent the major sink for material in the oceans. The
main pathway to the sediments is the deposition of suspended particles.
Such particles may be only in transit through the ocean from a conti-
nental origin or be formed in situ by chemical and biological processes.
Sinking particles can scavenge material from solution. Accordingly, this
section introduces the components found in marine sediments, but
emphasises processes that occur within the water column that lead to
the formation and alteration of the deposited material.
Marine sediments cover the ocean floor to a thickness averaging
500 m. The deposition rates vary with topography. The rate may be
several millimetres per year in nearshore shelf regions, but is only from
0.2 to 7.5 mm per 1000 years on the abyssal plains. Oceanic crustal
material is formed along spreading ridges and moves outwards eventu-
ally to be lost in subduction zones, the major trenches in the ocean.
Because of this continual movement, the sediments on the seafloor are
no older than Jurassic in age, about 166 million years.
The formation of marine sediments depends upon chemical, biolog-
ical, geological and physical influences. There are four distinct processes
that can be readily identified. Firstly, the source of the material obvi-
ously is important. This is usually the basis for classifying sediment
components and will be considered below in more detail. Secondly, the
material and its distribution on the ocean floor are influenced by its
transportation history, both to and within the ocean. Thirdly, there is
the deposition process that must include particle formation and altera-
tion in the water column. Finally, the sediments may be altered after
deposition, a process known as diagenesis. Of particular importance are
reactions leading to changes in the redox state of the sediments.
The components in marine sediments are classified according to
origin. Examples are given in Table 6. Lithogenous (or terrigenous)
material comes from the continents as a result of weathering processes.
210 Chapter 4
The relative contribution of lithogenous material to the sediments will
depend on the proximity to the continent and the source strength of
material derived elsewhere. The most important components in the
lithogenous fraction are quartz and the clay minerals (kaolinite, illite,
montmorillonite and chlorite). The distribution of the clay minerals
varies considerably. Illite and montmorillonite tend to be ubiquitous in
terrestrial material, but the latter has a secondary origin associated with
submarine volcanic activity. Kaolinite typifies intense weathering ob-
served in tropical and desert conditions. Therefore, it is relatively
enriched in equatorial regions. On the other hand, chlorite is indicative
of the high-latitude regimes where little chemical weathering occurs. The
lithogenous components tend to be inert in the water column and
represent detrital deposition. Nonetheless, the particle surfaces can act
as important sites for adsorption of organic material and trace elements.
Hydrogenous components, also known as chemogenous or halmeic
material, are those produced abiotically within the water column. This
may comprise primary material formed directly from seawater upon
exceeding a given solubility product, termed authigenic precipitation.
The best-known examples of authigenic material are the various types of
ferromanganese nodules found throughout the oceans. Alternatively,
Table 6 The four categories of marine sedimentary components with examples
of mineral phases
Classification Mineral example Chemical formula
Lithogenous Quartz SiO
2
Microcline KA1Si
3
O
8
Kaolinite Al
4
Si
4
O
10
(OH)
8
Montmorillonite Al
4
Si
8
O
20
(OH)
4
nH
2
O
Illite K
2
Al
4
(Si, Al)
8
O
20
(OH)
4
Chlorite (Mg,Fe
21
)
10
Al
2
(Si,Al)
8
O
20
(OH,F)
16
Hydrogenous Fe–Mn mineral FeO(OH) – MnO
2
Carbonate fluoroapatite Ca
5
(PO
4
)
3÷x
(CO
3
)
x
F
11x
Barite BaSO
4
Pyrite FeS
2
Aragonite CaCO
3
Dolomite CaMg(CO
3
)
2
Biogenous Calcite CaCO
3
Aragonite CaCO
3
Opaline silica SiO
2
nH
2
O
Apatite Ca
5
(F,Cl) (PO
4
)
3
Barite BaSO
4
Organic matter
Cosmogenous Cosmic spherules
Meteoric dusts
Source: adapted from Harrison and de Mora, 1996.
23
211 Chemistry of the Oceans
secondary material may be formed as components of continental or
volcanic origin become altered by low-temperature reactions in seawa-
ter, a mechanism known as halmyrolysis. Halmyrolysis reactions can
occur in the estuarine environment, being essentially an extension of
chemical weathering of lithogenous components. Such processes con-
tinue at the sediment–water interface. Accordingly, there are consider-
able overlaps between the terms weathering, halmyrolysis and
diagenesis. Owing to the importance that surface chemistry has on the
final composition, authigenic precipitation and halmyrolysis are con-
sidered further in Section 4.3.2.
Biogenous (or biotic) material is produced by the fixation of mineral
phases by marine organisms. The most important phases are calcite and
opaline silica, although aragonite and magnesian calcite are also deposited.
As indicated in Table 7, several plants and animals are involved, but the
planktonic organisms are the most important with respect to the World
Ocean. The source strength depends upon the biological species compo-
sition and productivity of the overlying oceanic waters. For instance,
siliceous oozes are found in polar latitudes (diatoms) and along the equator
(radiolaria). The relative contribution of biogenous material to the sedim-
ents depends upon its dilution by material from other sources and the
extent to which the material can be dissolved in seawater. As noted
previously, both calcareous and siliceous skeletons are subject to consid-
erable dissolution in the water column and at the sediment–water interface.
There are two sources that give rise to minor components in the marine
sediments. Cosmogenous material is that derived from an extra-terrestrial
source. Such material tends to comprise small (i.e., o0.5 mm) black
Table 7 Quantitatively important plants and animals that secrete calcite, arag-
onite, Mg-calcite, and opaline silica
Mineral Plants Animals
Calcite Coccolithophorids
a
Foraminifera
a
Molluscs
Bryozoans
Aragonite Green algae Molluscs
Corals
Pteropods
a
Bryozoans
Mg-calcite Coralline (red) algae Benthic foraminifera
Echinoderms
Serpulids (tubes)
Opaline silica Diatoms
a
Radiolaria
a
Sponges
a
Planktonic organisms
Source: adapted from Berner and Berner, 1987.
24
212 Chapter 4
micrometeorites or cosmic spherules. The composition is either magnetite
or a silicate matrix including magnetite. They are ubiquitous but scarce,
with relative contributions to the sediments decreasing with an increase in
sedimentation rate. Finally, there are anthropogenic components, notably
heavy metals and Sn, which can have a significant influence on sediments
in coastal environments.
As noted in Section 4.1.1, the principal modes of transport of partic-
ulate material to the ocean are by rivers or via the atmosphere. Within
the oceans, distribution is further affected by ice rafting, turbidity
currents, organisms and oceanic currents. Turbidity currents refer to
the turbid and turbulent flow of sediment-laden waters along the sea-
floor caused by sediment slumping. They are especially important in
submarine canyons and can transport copious amounts of material,
including coarse-grained sediments, to the deep sea. Ice rafting can also
transport substances to the deep sea. Although, ice rafting is presently
confined to the polar latitudes (401N and 551S), there have been con-
siderable variations in ice limits within the geologic record. Organisms
are notable not only for biogenous sedimentation, but also they can
influence fine-grained lithogenous material that becomes incorporated
into faecal pellets consequently accelerating the settling rate. Ocean
currents are important for the distribution of material with a long
residence time. Major surface currents are zonal and tend to reinforce
the pattern of aeolian supply. On the other hand, deepwater currents are
of little consequence as velocities are slow relative to the settling rates.
4.3.2 Surface Chemistry of Particles
4.3.2.1 Surface Charge. Parcles in seawater tend to exhibit a negative
surface charge. There are several mechanisms by which this might arise.
Firstly, the negative charge can result from crystal defects (i.e., vacant
cation positions) or cation substitution. Clay minerals are layered
structures of octahedral AlO
6
and tetrahedral SiO
4
. Either substitution
of Mg(II) and Fe(II) for the Al(III) in octahedral sites or replacement of
Si(IV) in tetrahedral location by Al(III) can cause a net negative charge.
Secondly, a surface charge can result from the differential dissolution of
an electrolytic salt such as barite (BaSO
4
). A charge will develop
whenever the rate of dissolution of cations and anions differs. Thirdly,
organic material can be negatively charged due to the dissociation of
acidic functional groups.
Adsorption processes can also lead to the development of a negatively
charged particle surface. One example is the specific adsorption of
anionic organic compounds onto the surfaces of particles. Another
213 Chemistry of the Oceans
mechanism relates to the acid–base behaviour of oxides in suspension.
Metal oxides (most commonly Fe, Mn) and clay minerals have frayed
edges on account of broken metal–oxygen bonds. The surfaces can be
hydrolysed and exhibit amphoteric behaviour
÷X ÷ O
÷
(s)
÷ H
÷
aq
= ÷X ÷ OH
(s)
÷X ÷ O
÷
(s)
÷ H
÷
aq
= ÷X ÷ OH
÷
2(s)
The hydroxide surface exhibits a different charge depending upon the
pH. Cations other than H
1
can act as the potential determining ion. The
point of zero charge (PZC) is the negative log of the activity at which the
surface exhibits no net surface charge. At the PZC
[÷X ÷ O
÷
(s)
[ = [÷X ÷ OH
÷
2(s)
[
The PZC for some mineral solids found in natural waters are shown in
Table 8. Clearly, the extent to which such surfaces can adsorb metal
cations will be dependent upon the pH of the solution. At the pH typical
of seawater, most of the surfaces indicated in Table 8 would be nega-
tively charged and would readily adsorb metal cations.
4.3.2.2 Adsorption Processes. Physical or non-specific adsorption in-
volves relatively weak attractive forces, such as electrostatic attraction
and van der Waals forces. Adsorbed species retain their co-ordinated
Table 8 The PZC for some mineral phases
Mineral pH
PZC
a-Al
2
O
3
9.1
a-Al
2
(OH)
3
5.0
g-AlOOH 8.2
CuO 9.5
Fe
3
O
4
6.5
a-FeOOH 7.8
g-Fe
2
O
3
6.7
‘Fe(OH)
3
’ (amorphous) 8.5
MgO 12.4
d-MnO
2
2.8
b-MnO
2
7.2
SiO
2
2.0
ZrSiO
4
5
Feldspars 2–2.4
Kaolinite 4.6
Montmorillonite 2.5
Albite 2.0
Chrysotile 412
Source: adapted from Stumm and Morgan, 1996.
14
214 Chapter 4
sphere of water and hence, cannot approach the surface closer than the
radius of the hydrated ion. Adsorption is favoured by ions having a high
charge density, i.e., trivalent ions in preference to univalent ones.
Additionally, an entropy effect promotes the physical adsorption of
polymeric species, such as Al and Fe oxides, because a large number of
water molecules and monomeric species is displaced.
Chemisorption or specific adsorption involves greater forces of at-
traction than physical adsorption. As hydrogen bonding or p–orbital
interactions are utilised, the adsorbed species lose their hydrated spheres
and can approach the surface as close as the ionic radius. Whereas
multilayer adsorption is possible in physical adsorption, chemisorption
is necessarily limited to monolayer coverage.
As outlined previously, hydrated oxide surfaces have sites that are
either negatively charged or readily deprotonated. The oxygen atoms
tend to be available for bond formation, a favourable process for
transition metals. Several mechanisms are possible. An incoming metal
ion, M
z1
, may eliminate an H
1
ion as
÷X ÷ O ÷ H ÷ M

= ÷X ÷ O ÷ M
(z-1)÷
÷ H
÷
Alternatively, two or more H
1
ions may be displaced, thereby forming a
chelate as
—X – O – H —X – O
+ M
z+
M
(z−2)+
+ 2H
+
—X – O – H —X – O
A metal complex, ML
n
z1
, may be co-ordinated instead of a free ion by
displacement of one or more H
1
ions in a manner analogous to the
above reaction. In addition, the metal complex might eliminate a
hydroxide group giving rise to a metal–metal bond as
÷X ÷ O ÷ H ÷ ML

n
= ÷X ÷ ML
(z-1)÷
n
÷ OH
÷
It should be noted that all of these reactions are equilibria for which an
appropriate equilibrium constant can be defined and measured. This
data can then be incorporated into the speciation models discussed in
Section 4.2.5.
4.3.2.3 Ion Exchange Reactions (see also Chapter 5). Both mineral
particles and particulate organic material can take up cations from
solution and release an equivalent amount of another cation into
solution. This process is termed cation exchange and the cation
215 Chemistry of the Oceans
exchange capacity (CEC) for a given phase is a measure of the number
of exchange sites present per 100 g of material. This is operationally
defined by the uptake of ammonium ions from 1 mol L
÷1
ammonium
acetate at pH 7. The specific surface area and CEC are given in Table 9
for several sorption-active materials.
There are several factors that influence the affinity of cations towards
a given surface. Firstly, the surface coverage will increase as a function
of the cation concentration. Secondly, the affinity for the exchange site is
enhanced as the oxidation state increases. Finally, the higher the charge
density of the hydrated cation, the greater will be its affinity for the
exchange site. In order of increasing charge density, the group I and II
cations are
BaoSroCaoMgoCsoRboKoNaoLi
4.3.2.4 Role of Surface Chemistry in Biogeochemical Cycling. Reac-
tions at the aqueous–particle interface have several consequences for
material in the marine environment, from estuaries to the deep-sea
sediment–water boundary. Within estuarine waters, suspended particles
experience a dramatic change in the composition and concentration of
dissolved salts. A number of halmyrolysates can be formed. Clay
minerals undergo cation exchange as Mg
21
and Na
1
replace Ca
21
and K
1
. Alternatively, montmorillonite may take up K
1
becoming
transformed to illite. Hydrogenous components, in particular Mn and
Fe oxides, may be precipitated onto the surfaces of suspended particles.
The particulate material generally accumulates organic coatings within
estuaries, which together with an increase in the ionic strength of the
surrounding solution, leads to the formation of stable colloids. Both the
oxide and organic coatings can subsequently scavenge other elements in
the estuary.
Table 9 The specific surface area and cation-exchange capacities of several
sorption-active materials
Material
Specific surface area
(mg
2
g
÷1
)
Cation-exchange capacity
(meq/100 g)
Calcite (o2 mm) 12.5 —
Kaolinite 10–50 3–15
Illite 30–80 10–40
Chlorite — 20–50
Montmorillonite 50–150 80–120
Freshly precipitated Fe(OH)
3
300 10–25
Amorphous silicic acid — 11–34
Humic acids from soils 1900 170–590
Source: adapted from Fo¨ rstner and Wittman, 1981.
25
216 Chapter 4
Within the ocean, the exchange of material from the dissolved to the
suspended particulate state influences the distribution of several ele-
ments. This scavenging process removes dissolved metals from solution
and accelerates their deposition. The effectiveness of this process is
obvious in the depth profiles of metals, especially those of the surface
enrichment type. Furthermore, the removal can be expressed in terms of
a deepwater scavenging residence time as indicated in Table 10.
The scavenging mechanism can be particularly effective in the water–
sediment boundary region. The re-suspension of fine sediments gener-
ates a very large surface area for adsorption and ion exchange processes.
Within the immediate vicinity of hydrothermal springs, reduced species
of Mn and Fe are released and subsequently are oxidised to produce
colloidal oxyhydroxides, which have a large surface area and very great
sorptive characteristics. Finally, ferromanganese nodules form at the
sediment–water interface and become considerably enriched in a num-
ber of trace metals via surface reactions.
Ferromanganese nodules result from the authigenic precipitation of
Fe and Mn oxides at the seafloor. Two morphological types are recog-
nised, depending upon the growth mechanism. Firstly, spherical encrus-
tations produced atop oxic deep-sea sediments grow slowly, accu-
mulating material from seawater. These seawater nodules exhibit a
relatively low Mn:Fe ratio and are especially enriched with respect to
Co, Fe and Pb. Secondly, discoid shaped nodules develop in nearshore
environments deriving material via diffusion from the underlying anoxic
sediments. Such diagenetic nodules grow faster than deep-sea varieties
and metals tend to be in lower oxidation states. They have a high Mn:Fe
ratio and enhanced content of Cu, Mn, Ni and Zn. Ferromanganese
nodules have concentric light and dark bands in cross-section, related to
Table 10 The deepwater scavenging residence times of some trace elements in
the oceans
Element
Scavenging residence time
(year) Element
Scavenging residence time
(year)
Sn 10 Mn 51–65
Th 22–33 Al 50–150
Fe 40–77 Sc 230
Co 40 Cu 385–650
Po 27–40 Be 3700
Ce 50 Ni 15 850
Pa 31–67 Cd 117 800
Pb 47–54 Particles 0.365
Source: adapted from Chester, 1990.
1
217 Chemistry of the Oceans
Fe and Mn oxides, respectively. Patterns of trace element enrichment in
the nodules are determined by mineralogy, the controlling mechanisms
being related to cation substitution in the crystal structure. Mn phases
preferentially accumulate Cu, Ni, Mo and Zn. Alternatively, Co, Pb, Sn,
Ti and V are enriched in Fe phases.
4.3.3 DIAGENESIS
Diagenesis refers to the collection of processes that alter the sediments
following deposition. These mechanisms may be physical (compaction),
chemical (cementation, mineral segregation, ion exchange reactions) or
biological (respiration). The latter are of particular importance as the
bacteria control pH and pe in the interstitial waters, which in turn affect
a wide range of chemical equilibria. These master variables influence the
composition of the interstitial water, and can exert a feedback effect on
the overlying seawater. Also, they can ultimately control the minera-
logical phases that are lost to the sediment sink.
Organic material accumulates with other sedimentary components at
the time of deposition. High biological productivity in surface waters and
rapid sedimentation ensures that most nearshore and continental margin
sediments contain significant amounts of organic matter. Biochemical
oxidation of this material exhausts the available O
2
creating anoxic
conditions. The oxic/anoxic boundary occurs at the horizon where the
respiratory consumption of O
2
balances its downward diffusion. Upon
depleting the O
2
, other constituents are used as oxidants leading to the
stepwise depletion of NO
3
÷
, NO
2
÷
and SO
4

. Thereafter, organic matter
itself may be utilised with the concurrent production of CH
4
.
This series of reactions causes progressively greater reducing condi-
tions, with consequent influences on the chemistry of several elements.
Metals are reduced and so are present in lower oxidation states. In
particular, Mn undergoes reductive dissolution from MnO
2s
to Mn
aq
21
.
The divalent state being much more soluble, Mn is effectively remobi-
lised under anoxic conditions and can be released back into overlying
seawater. As seen in the previous section, this is one pathway to
ferromanganese nodule formation. This can also be true for other
elements that had been deposited following incorporation into the Fe
and Mn oxide phases. In contrast, some elements can be preserved very
effectively in anoxic sediments. Interstitial waters in marine sediments,
in contrast to freshwater deposits, have high initial concentrations of
SO
4

. Bacterial sulfate reduction proceeds via the reaction
2CH
2
O ÷ SO

4
= H
2
S ÷ 2HCO
÷
3
218 Chapter 4
Thus, sulfide levels in interstitial waters increase. A number of elements
form insoluble sulfides, which under these anoxic conditions are pre-
cipitated and retained within the sediments. A notable example is the
accumulation of pyrite, FeS
2
, but also Ag, Cu, Pb and Zn are enriched in
anoxic sediments in comparison with oxic ones.
4.4 PHYSICAL AND CHEMICAL PROCESSES IN ESTUARIES
Rivers transport material in several phases: dissolved, suspended par-
ticulate and bed load. Physical and chemical processes within an estuary
influence the transportation and transformation of this material, thereby
affecting the net supply of material to the oceans. Several definitions and
geomorphologic classifications of estuaries have been reviewed by Pe-
rillo (1995).
26
From a chemical perspective, an estuary is most simply
described as the mixing zone between river water and seawater charac-
terised by sharp gradients in the ionic strength and chemical composi-
tion. Geographic distinctions can be made between drowned river
valleys, fjords and bar-built estuaries. They can alternatively be classi-
fied in terms of the hydrodynamic regime as:
(i) salt wedge,
(ii) highly stratified,
(iii) partially stratified, and
(iv) vertically well mixed.
The aqueous inputs into the system are the river flow and the tidal prism.
The series above is ranked according to the diminishing importance of
the riverine flow and the increasing marine contribution. Thus, a salt
wedge estuary represents the extreme case dominated by river flow, in
which very little mixing occurs. A fresh, buoyant layer flows outward
over denser, saline waters. In contrast, the vertically well-mixed estuary
is one dominated by the tidal prism. The inflowing river water mixes
thoroughly with and dilutes the seawater, but the effective dilution
diminishes with distance along the mixing zone.
The position of the mixing zone in the estuary exhibits considerable
temporal variations. There can be a strong seasonal effect, largely due to
non-uniform river discharge. High winter rainfall leads to a wintertime
discharge maximum. However, winter precipitation as snow creates a
storage reservoir, such that the river flow maximum occurs following
snow melt in spring or even early summer if the catchment area is of high
elevation as for the Fraser River in western Canada. On shorter time-
scales, the mixing zone is influenced by tidal cycles. Thus, the penetra-
tion of seawater into the estuary depends upon the spring–neap tidal
219 Chemistry of the Oceans
cycle and the diurnal nature of the tides. Together these influences
determine the geographic extent of sediments experiencing a variable
salinity regime. Variations in the river discharge affect the mass loading
of the discharge, both in terms of suspended sediment and bed load
material. The hydrodynamic regime in the estuary influences the depo-
sition of the riverine sedimentary material and the mixing of dissolved
material.
The estuary is a mixing zone for river water and seawater, the
characteristics of which differ considerably. River water is slightly acidic
and of low ionic strength with a salt matrix predominantly of Ca(H-
CO
3
)
2
(B120 mg L
÷1
). In contrast, seawater has a higher pH (B8),
higher ionic strength (B0.7) and consists primarily of NaCl (B35 g
L
÷1
). As a consequence, the salt matrix within the estuary is dominated
by the sea salt end member throughout the mixing zone except for a
small proportion at the dilute extreme. Salinity can be used as a
conservative index, although conductivity is better, not being subject
to systematic conversion errors in the initial mixing region.
In a plot of concentration vs. some conservative index (i.e., S%, Cl% or
conductivity), the theoretical dilution curve would comprise a straight line
between the river and seawater end members. A dissolved constituent that
exhibits such a distribution is said to behave conservatively in the estuary.
Whereas a negative slope shows that the riverine end member is progres-
sively diluted during mixing with seawater, a positive slope indicates that
the seawater end member has the greater concentration. Conservative
behaviour is exhibited, for example, by Na
1
, K
1
and SO
4

. Reactive
silica may at times behave conservatively. Non-conservative behaviour
can result from an additional supply of material (i.e., causing positive
deviations from the theoretical dilution curve). Elements that may show a
maximum concentration at some intermediate salinity are Mn and Ba.
Alternatively, the removal of dissolved material during mixing (i.e.,
negative deviation from the theoretical dilution curve) can be caused by
biological activity or by dissolved to particulate transformations. Biolog-
ical activity can cause non-conservative behaviour for nutrient elements,
including reactive silica. Dissolved constituents typically transformed to
the particulate phase include Al, Mn and Fe (see Figure 14) in some
estuaries. The pH distribution is usually characterised by a pH minimum
in the initial mixing zone, resulting from the non-linear salinity depend-
ence of the first and second dissociation constants of H
2
CO
3
. Notwith-
standing the obvious utility of component–conservative index plots, they
can be applied and interpreted only with caution. Often it is difficult to
define the exact composition of the end members. Hence, a plot that
apparently denotes non-conservative behaviour could arise if temporal
220 Chapter 4
fluctuations in the concentration of the component of interest occur on
the same relative time scales as estuarine flushing.
A component can undergo considerable physico-chemical speciation
alterations in an estuary. With respect to dissolved constituents, the
composition and concentration of available ligands changes. Depending
upon the initial pH of the riverine water, OH
÷
may become markedly
more important down the estuary. Similarly, chlorocomplexes for met-
als such as Cd, Hg and Zn become more prevalent as the salinity
increases. Conversely, the competitive influence of seawater derived Ca
and Mg for organic material decreases the relative importance of humic
complexation for Mn and Zn.
Estuaries are particularly well known for dissolved–particulate interac-
tions. Such changes in phase come about via several mechanisms. Firstly,
dissolution–precipitation processes may occur. This is especially impor-
tant for the authigenic precipitation of Fe and Mn oxyhydroxides.
Secondly, components may experience adsorption–desorption reactions.
Desorption can occur in the initial mixing zone, partly in response to the
pH minimum. Adsorption, particularly in association with the Fe and Mn
phases, can accumulate material within the suspended sediments. Thirdly,
flocculation and aggregation processes can remove material from solu-
tion. This occurs as particulate material with negatively charged surfaces
adsorb cations in the estuary. The surface charge diminishes and as the
ionic strength increases, the particles experience less electrostatic repul-
sion. Eventually, the situation arises whereby particle collisions lead to
aggregation due to weak bonding. This process can be facilitated if
particle surfaces are coated with organic material (then known as
flocculation rather than aggregation). The three types of processes out-
lined above often happen simultaneously in the estuarine environment.
Dissolved Fe, as shown in Figure 14, typifies such non-conservative
behaviour. The transformation of dissolved into particulate phases can
then be followed by deposition to the estuarine sediments. Thus, the flux
of material to the ocean can be considerably modified, particularly as such
sediments may be transported landward rather than seaward.
Biological activity in the estuarine environment can also influence the
speciation of constituents, notably dissolved–particulate partitioning. A
complex regeneration cycle determines distributions and modifies the
riverine flux. This is especially the case for nutrients, and estuaries are
often termed a nutrient trap. Estuaries tend to be regions of high biological
productivity as rivers have elevated nutrient concentrations. Moreover,
several freshwater organisms die upon encountering brackish water with
consequent cell rupture and the release of contents into solution. Regard-
less of the source, the nutrients stimulate phytoplankton productivity.
221 Chemistry of the Oceans
Whereas some of the biological material (either transported via the fresh-
water or produced in situ within the estuarine zone) can be flushed out to
sea, the remainder settles out of the surface water to be deposited onto the
floor of the estuary. Respiration of this debris by benthic organisms
regenerates nutrients and any contaminants that have been accumulated,
releasing them into the bottom water. In estuaries where a two-layer flow
is well defined, these nutrients are transported upriver in the salt wedge
and entrained into the exiting river water, thereby adding to the available
nutrient pool. Polluted rivers having a high nutrient loading are subject to
eutrophication due to over-stimulation of biological activity. Anoxic
conditions within the bottom waters and/or underlying sediments can
result, depending upon the organic loading. Aeolian transport of nitrate to
Chesapeake Bay can lead to low O
2
conditions. As mentioned previously,
some fjords develop anoxic conditions when bottom waters stagnate due
to limited mixing.
10
1
2
D
i
s
s
o
l
v
e
d

F
e

(
µ
m
o
l
/
k
g
)
3
4
5
6
20
Salinity (‰)
Taieri estuary
30
Figure 14 The distribution of dissolved Fe vs. Salinity in the Taieri Estuary, New
Zealand; v 21 October 1980, 4 December 1980
(Adapted from Hunter, 1983.
27
)
222 Chapter 4
4.5 MARINE CONTAMINATION AND POLLUTION
Both contamination and pollution entail the perturbation of the natural
state of the environment by anthropogenic activity. The two terms are
distinguishable in terms of the severity of the effect, whereby pollution
induces the loss of potential resources.
28
Additionally, a clear cause–
effect relationship must be established for a substance to be classified as
a pollutant towards a particular organism. The human-induced distur-
bances take many forms, but the greatest effects tend to be in coastal
environments due to the source strengths and pathways. Waters and
sediments in coastal regions bear the brunt of industrial and sewage
discharges, and are also subject to dredging and spoil dumping. Agri-
cultural runoff may contain pesticide residues and elevated nutrients, the
latter of which may over-stimulate biological activity producing eutro-
phication and anoxic conditions. The deep sea has not escaped contam-
ination. The most obvious manifestations comprise crude oil, petroleum
products and plastic pollutants, but include the long-range transport of
long-lived radionuclides from coastal sources. Additionally, the aeolian
transport of heavy metals has enhanced natural fluxes of some elements,
particularly lead. Three case studies are introduced below to illustrate
diverse aspects of marine contamination and pollution.
4.5.1 Oil Slicks
Major releases of oil have been caused by the grounding of tankers (i.e.,
Torrey Canyon, Southwest England, 1967; Argo Merchant, Nantucket
Shoals, USA, 1976; Amoco Cadiz, Northwest France, 1978; Exxon
Valdiz, Alaska, 1990; Erika, France, 1999; Prestige, Spain, 2002) and
by the accidental discharge from offshore platforms (i.e., Chevron MP-
41C, Mississippi Delta, 1970; Ixtox I, Gulf of Mexico, 1979). Because oil
spills receive considerable public attention and provoke substantial
anxiety, oil pollution must be put into perspective. Crude oil has been
habitually introduced into the marine environment from natural seeps at
a rate of approximately 340 × 10
6
L y
÷1
. Anthropogenic activity has
recently augmented this supply by an order of magnitude; however,
most of this additional oil has originated from relatively diffuse sources
relating to municipal runoff and standard shipping operations. Excep-
tional episodes of pollution occurred in the Persian Gulf in 1991 (910 ×
10
6
L y
÷1
) and due to the Ixtox I well in the Gulf of Mexico in 1979 (530
× 10
6
L y
÷1
). In contrast to such mishaps, the Amoco Cadiz discharged
only 250 × 10
6
L y
÷1
of oil in 1978 accounting for the largest spill from a
tanker. The cumulative pollution from tanker accidents on an annual
223 Chemistry of the Oceans
basis matches that emanating from natural seepage. Nevertheless, the
impacts can be severe when the subsequent slick impinges on coastal
ecosystems.
Regardless of the source, the resultant oil slicks are essentially surface
phenomena that are affected by several transportation and transforma-
tion processes.
29
With respect to transportation, the principal agent for
the movement of slicks is the wind, but length scales are important.
Whereas small weather systems, such as thunderstorms, tend to disperse
the slick, cyclonic systems can move the slick essentially intact. Waves
and currents also affect the advection of an oil slick. To a more limited
extent, diffusion can act to transport the oil.
Transformation of the oil involves phase changes and degradation.
Several physical processes can invoke phase changes. Evaporation of the
more volatile components is a significant loss mechanism, especially for
light crude oil. The oil slick spreads as a buoyant lens under the influence
of gravitational forces, but generally separates into distinctive thick and
thin regions. Such pancake formation is due to the fractionation of the
components within the oil mixture. Sedimentation can play a role in
coastal waters when rough seas bring dispersed oil droplets into contact
with suspended particulate material and the density of the resulting
aggregate exceeds the specific density of seawater. Colloidal suspensions
can consist of either water-in-oil or oil-in-water emulsions, which behave
distinctly differently. Water-in-oil emulsification creates a thick, stable
colloid that can persist at the surface for months. The volume of the slick
increases and it aggregates into large lumps known as ‘‘mousse’’, thereby
acting to retard weathering. Conversely, oil-in-water emulsions com-
prise small droplets of oil in seawater. This aids dispersion and increases
the surface area of the slick, which can subsequently accelerate weath-
ering processes.
Chemical transformations of oil are evoked primarily through pho-
tochemical oxidation and microbial biodegradation. Not only is the
latter more important in nature, but strategies can be adopted to
stimulate biological degradation, consequently termed bioremediation.
All marine environments contain microorganisms capable of degrading
crude oil. Furthermore, most of the molecules in crude oils are suscep-
tible to microbial consumption. Oil contains little nitrogen or phospho-
rus and therefore, microbial degradation of oil tends to be nutrient
limited. Bioremediation often depends upon on the controlled and
gradual delivery of these nutrients, while taking care to limit the con-
current stimulation of phytoplankton activity. Approaches that have
been adopted are the utilisation of slow-release fertilisers, oleophilic
nutrients and a urea-foam polymer fertiliser incorporating oil-degrading
224 Chapter 4
bacteria. Bioremediation techniques were successfully applied in the
clean up of Prince William Sound and the Gulf of Alaska following the
Exxon Valdez accident. Alternative bioremediation procedures relying
on the addition of exogenous bacteria have still to be proved. Similarly,
successful bioremediation of floating oil spills has yet to be demon-
strated.
Source apportionment of crude oil in seawater and monitoring the
extent of weathering and biodegradation constitute important chal-
lenges in environmental analytical chemistry. As the concentration of
individual compounds varies from one sample of crude oil to another,
the relative amounts define a signature characteristic of the source.
Compounds that degrade at the same rate stay at fixed relative amounts
throughout the lifetime of an oil slick. Hence, a ‘‘source ratio’’, which
represents the concentration ratio for a pair of compounds exhibiting
such behaviour remains constant. Conversely, a ‘‘weathering ratio’’
reflects the concentration ratio for two compounds that degrade at
different rates and consequently continually changes. Oil spill monitor-
ing programmes conventionally determine four fractions
30
:
(i) volatile hydrocarbons;
(ii) alkanes;
(iii) total petroleum hydrocarbons; and
(iv) polycyclic aromatic hydrocarbons (PAHs).
The volatile hydrocarbons, albeit comparatively toxic to marine organ-
isms, evaporate relatively quickly and hence serve little purpose as
diagnostic aids. The alkanes and total petroleum hydrocarbons make
up the bulk of the crude oil. They can be used to some extent for source
identification and monitoring weathering progress. The final fraction,
the PAHs, comprises only about 2% of the total content of crude oil
but includes compounds that are toxic. Moreover, these components
exhibit marked disparities in weathering behaviour due to differences in
water solubility, volatility and susceptibility towards biodegradation. As
demonstrated in Figure 15, both a source ratio (C3-dibenzothiophenes/
C3-phenanthrenes) and a weathering ratio (C3-dibenzothiophenes/
C3-chrysenes) have been defined from among such compounds that
enable the extent of crude oil degradation to be estimated in the marine
environment, as well as for sub-tidal sediments and soils.
30
The discussion above focuses on petroleum hydrocarbons from oil
spills, representing just one source of contamination. Marine contami-
nant surveys are conducted not just in response to tanker accidents, but
routinely as a means to assess the quality of the marine environment.
Although analytical difficulties with environmental samples persist and
225 Chemistry of the Oceans
much material can only be classified as an unresolved complex mixture
(UCM), many individual aliphatic and aromatic compounds can be
routinely determined. Total petroleum hydrocarbon distributions, as
shown in Figure 16 for the Caspian Sea, provide evidence of pollution
‘‘hot spots’’.
31
In this case, the highest concentrations were observed in
Azerbaijan. Given that several individual PAHs can be ascribed to
different origins, plots of the relative amounts allows an assessment to
be made of the relative importance of petrogenic (fossil oil), pyrolytic
(combustion products) and natural (in situ biological activity) sources.
As shown in Figure 17, most of the PAHs in the Caspian Sea sediments
were derived from fossil oil.
31
This technique cannot distinguish between
material derived from natural seeps or anthropogenic activity. Other-
wise, the contribution of combustion products was evident in Russia and
natural sources were only observed in the Iranian sector.
4.5.2 Plastic Debris
The accumulation of litter and debris along shorelines epitomises a
general deterioration of environmental quality on the high seas. The
material originates not only from coastal sources, but also from the
ancient custom of dumping garbage from ships. Drilling rigs and
offshore production platforms have similarly acted as sources of con-
tamination. Some degree of protection in recent years has accrued from
both the London Dumping Convention (LDC) and the International
Figure 15 Plot of weathering ratio (C3-dibenzothiophenes/C3-chrysenes) vs. source ratio
(C3-dibenzothiophenes/C3-phenanthrenes) for fresh and degraded oil samples
from three different crude oil spills
(Adapted from Douglas et al., 1996.
30
)
226 Chapter 4
Convention for the Prevention of Pollution from Ships (MARPOL) that
outlaw such practices. However, the problem of seaborne litter remains
global in extent and not even Antarctica has been left unaffected.
32
The debris consists of many different materials, which tending to be
non-degradable endures in the marine environment for many years. The
most notorious are the plastics (e.g., bottles, sheets, fishing gear, pack-
aging materials and small pellets), but also includes glass bottles, tin
cans and lumber. This litter constitutes an aesthetic eyesore on beaches,
but more importantly can be potentially lethal to marine organisms.
Deleterious impacts on marine birds and mammals result from entan-
glement and ingestion. Lost or discarded plastic fishing nets remain
functional and can continue ‘‘ghost fishing’’ for several years. This is
similarly true for traps and pots that go astray. Plastic debris settling on
soft and hard bottoms can smother benthos and limit gas exchange with
Figure 16 Distribution of total hydrocarbons (total aliphatic and aromatic) in sediments
from the Caspian Sea (mg g
÷1
dry wt)
(From Tolosa et al., 2004.
31
)
227 Chemistry of the Oceans
pore waters. Despite the negative effects of seaborne plastic debris, this
material can have positive consequences serving as new habitats for
opportunistic colonisers.
4.5.3 Tributyltin
Tributyltin (TBT) provides an interesting case study of a pollutant in the
marine environment.
33
Because TBT compounds are extremely poison-
ous and exhibit broad-spectrum biocidal properties, they have been
utilised as the active ingredient in marine anti-fouling paint formula-
tions. Its potency and longevity ensures good fuel efficiencies for ship
operations and guarantees a long lifetime between repainting. TBT-
based paints have been used on boats of all sizes, from small yachts to
supertankers, ensuring the global dispersion of TBT throughout the
marine environment, from the coastal zone to the open ocean.
Notwithstanding such benefits, the extreme toxicity and environmental
persistence has resulted in a wide range of deleterious biological effects on
non-target organisms. TBT is lethal to some shellfish at concentrations as
low as 0.02 mg TBT-SnL
÷1
. Lower concentrations result in sub-lethal
effects, such as poor growth rates and reduced recruitment leading to the
decline of shellfisheries. The most obvious manifestations of TBT con-
tamination have been shell deformation in Pacific oysters (Crassostrea
gigas), and the development of imposex (i.e., the imposition of male sex
organs on females) in marine gastropods. The later effect has caused
dramatic population decline of gastropods at locations throughout the
Figure 17 Ternary diagram showing the relative amounts of PAHs from different sources
(fossil oil, combustion products and natural biological activity) and distin-
guished on a country basis
(From Tolosa et al., 2004.
31
)
228 Chapter 4
world. TBT has been observed to accumulate in fish and various marine
birds and mammals, with yet unknown consequences. Although it has not
been shown to pose a public health risk, one recent study reported
measurable butyltin concentrations in human liver.
34
The economic consequences of the shellfisheries decline led to a rapid
political response globally. The first publication
35
suggesting TBT to be
the causative agent appeared in only 1982, and led to prompt legislative
action. France was the first country to control the use of TBT-based
paints, in the first instance on boats o25 m in length at some coastal
locations. Oyster aquaculture in Arcachon Bay benefited immediately,
with a notably decline in shell deformations and TBT-body burdens,
and the complete recovery of production within two years (Figure 18).
Several other countries introduced various controls and bans on these
marine anti-foulants. Comparable improvements in oyster conditions
were subsequently observed in Great Britain and Australia. Similarly,
there have been many reported instances of restoration of gastropod
populations at previously impacted locations. Certainly the TBT flux to
the marine environment decreased, as manifested in sedimentary TBT
profiles. However, most of the legislation first introduced applied only to
small vessels and large ships continued to act as a source of TBT to the
marine environment. Imposexed gastropods were observed at sites (e.g.,
North Sea and Strait of Malacca) where the source of TBT could only
Figure 18 Annual oyster (Crassostrea gigas) production in Arcachon Bay, 1978–1985;
Restrictions on TBT use were applied starting January 1982
(Data from Alzieu, 1991.
36
)
229 Chemistry of the Oceans
have been attributed to shipping. Global concern was sufficiently great
that in 2001 the International Maritime Organisation (IMO) success-
fully negotiated the International Convention on the Control of Harmful
Anti-fouling Systems on Ships. The Convention aims to ban the appli-
cation of organotin-based anti-fouling paints on ships from 2003 and
their presence on ship hulls from 2008, but does require ratification of 25
countries comprising 25% of the world’s merchant shipping tonnage
before coming into effect.
TBT exists in solution as a large univalent cation and forms a neutral
complex with Cl
÷
or OH
÷
. It is extremely surface active and so is readily
adsorbed onto suspended particulate material. Such adsorption and
deposition to the sediments limits its lifetime in the water column.
Degradation, via photochemical reactions or microbially mediated
pathways, obeys first-order kinetics. Several marine organisms, as di-
verse as phytoplankton to starfish, debutylate TBT. Stepwise debutylat-
ion produces di- and mono-butyltin, which are much less toxic in the
marine environment than is TBT. As degradation rates in the water
column are on the order of days to weeks, they are slow relative to
sedimentation. TBT accumulates in the sediments where degradation
rates are much slower, with the half-life being on the order of years.
37
Furthermore, concentrations are highest in those areas, such as marinas
and harbours, which are most likely to undergo dredging. The intrinsic
toxicity of TBT, its persistency in the sediments and its periodic remo-
bilisation by anthropogenic activity are likely to retard the long-term
recovery of the marine ecosystem.
Although the unrestricted use of TBT should end, significant chal-
lenges remain in many parts of the world. For the most part, the coastal
tropical ecosystems remain unprotected and the sensitivity of its indig-
enous organisms relatively poorly evaluated. TBT endures in sediments
globally, with concentrations usually greatest in environments most
likely to be perturbed, such as ports and marinas. The widespread
introduction of TBT into seawater will continue from vessels not yet
subject to legislation until at least 2008, depending on when the IMO
Convention comes into force. However, the paramount lesson learned
from TBT should be that potential replacement compounds must be
properly investigated prior to their introduction in order to avoid
another global pollution experiment.
QUESTIONS
(i) What are the main sources and sinks for dissolved and partic-
ulate metals entering the ocean?
230 Chapter 4
(ii) Define residence time and outline the factors that influence the
residence time of an element in the ocean. Provide examples of
oceanic residence times for elements that span the time scale.
(iii) Define salinity. What are the notable variations in sea salt, in
terms of concentration and composition, in the world ocean?
(iv) Using data available in Table 4, calculate the concentration of
H
2
CO
3
in seawater at 51C in equilibrium with atmospheric CO
2
at 370 ppm.
(v) Calculate the speciation of H
2
S in seawater at pH 8.3 at 251C
given that pK
1
= 7.1 and pK
2
= 17.0.
(vi) Explain how DMS of marine origin might affect global climate.
(vii) What are the major nutrients in the ocean? Describe their
concentration profiles and account for any differences between
them according to chemical behaviour.
(viii) Describe the different types of depth profiles that various metals
exhibit and explain how differences in their profiles originate.
(ix) Assuming all g
/
s = 1, calculate the speciation of lead in seawater
at 251C given the following values for stability constants for the
chlorocomplexes (K
1
= 10
7.82
, b
2
=10
10.88
, b
3
= 10
13.94
, b
4
=
10
16.30
). Note that [Cl
÷
] is 0.559 mmol L
÷1
.
(x) With specific reference to Question 9, outline the potential
limitations of using equilibrium models to explain chemical
behaviour of trace metals in seawater.
(xi) Describe the classification of marine sediments and give exam-
ples of each sediment type.
(xii) Why do suspended particles exhibit a surface charge and how
could this characteristic moderate the composition of ocean’s
waters?
(xiii) With respect to estuarine chemistry, describe conservative and
non-conservative behaviour and provide examples of cationic
and anionic species for each category.
(xiv) What natural processes are responsible for weathering an oil slick?
(xv) Why is tributyltin considered such a potent pollutant in the
marine environment?
REFERENCES
1. R. Chester, Marine Geochemistry, Unwin Hyman, London, 1990, 698.
2. P. Tchernia, Descriptive Regional Oceanography, Pergamon Press,
Oxford, 1980, 253.
231 Chemistry of the Oceans
3. The Open University, Seawater: Its Composition, Properties and
Behaviour, Open University, Oxford, 1989, 165.
4. K.S. Stowe, Ocean Science, Wiley, New York, 1979.
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6. D. Dyrssen and M. Wedborg, in The Sea, E. Goldberg (ed), Wiley,
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7. P. Brewer, in Chemical Oceanography, 2nd edn, vol. 1, J.P. Riley
and G. Skirrow (eds), Academic Press, London, 1975, 415.
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Chester (eds), Academic Press, London, 1983, 157.
9. R.F. Weiss, Deep-Sea Res., 1970, 17, 721.
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G. Skirrow (eds), Academic Press, London, 1975, 497.
11. W.S. Broecker and T.H. Peng, Tracers in the Sea, Lamont-Doherty
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12. P.S. Liss, in Air–Sea Exchange of Gases and Particles, P.S. Liss and
W.G.N. Slinn (eds), Reidel, Dordrecht, 1983, 241.
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14. W. Stumm and J.J. Morgan, Aquatic Chemistry, 3rd edn, Wiley,
New York, 1996, 1022.
15. J. Lovelock, Gaia. A New Look at Life on Earth, Oxford University
Press, Oxford, 1979.
16. R.J. Charlson, J.E. Lovelock, M.O. Andreae and S.G. Warren,
Nature, 1987, 326, 655.
17. M.O. Andreae, in The Role of Air–Sea Exchange in Geochemical
Cycling, P. Buat-Me´ nard (ed), Reidel, Dordrecht, 1986, 331.
18. A.C. Redfield, Am. J. Sci., 1958, 46, 205.
19. E. Goldberg, M. Koide, J.S. Yang and K.K. Bertine, Metal Speciat-
ion: Theory, Analysis and Applications, J.R. Kramer and H.E. Allen
(eds), Lewis Publishers, Chelsea, 1988.
20. L. O
¨
hman and S. Sjo¨ berg, in Metal Speciation: Theory, Analysis and
Applications, J.R. Kramer and H.E. Allen (eds), Lewis Publishers,
Chelsea, 1988, 1.
21. S.J. de Mora and R.M. Harrison, in Hazard Assessment of Chem-
icals, Current Developments, vol 3, J. Saxena (ed), Academic Press,
London, 1984, 1.
22. P. Craig, Organometallic Compounds in the Environment, P.S. Craig
(ed), Longman, Harlow, 1986, 1.
232 Chapter 4
23. R.M. Harrison and S.J. de Mora, Introductory Chemistry for the
Environmental Sciences, 2nd edn, Cambridge University Press,
Cambridge, 1996, 373.
24. E.K. Berner and R.A. Berner, The Global Water Cycle, Prentice-
Hall, NJ, 1987, 397.
25. U. Fo¨ rstner and G.T.W. Wittman, Metal Pollution in the Aquatic
Environment, 2nd edn, Springer, Berlin, 1981, 486.
26. G.M.E. Perillo, in Geomorphology and Sedimentology of Estuaries,
G.M.E. Perillo (ed), Elsevier Science, Amsterdam, 1995, 17.
27. K. Hunter, Geochim. Cosmochim. Acta, 1983, 47, 467.
28. E. Goldberg, Mar. Pollut. Bull., 1992, 25, 45.
29. S. Murray, in Pollutant Transfer and Transport in the Sea, vol. 2, G.
Kullenberg (ed), CRC Press, Boca Raton, 1982, 169.
30. G.S. Douglas, A.E. Bence, R.C. Prince, S.J. McMillen and E.L.
Butler, Environ. Sci. Technol., 1996, 30, 2332.
31. I. Tolosa, S.J. de Mora, M.R. Sheikholeslami, J.-P. Villeneuve, J.
Bartocci and C. Cattini, Mar. Pollut. Bull., 2004, 48, 44–60.
32. M.R. Gregory and P.G. Ryan, in Marine Debris: Sources, Impacts
and Solutions, J.M. Coe and D.B. Rogers (eds), Springer, New
York, 1996, 49.
33. S.J. de Mora (ed.), Tributyltin: Case Study of an Environmental
Contaminant, Cambridge University Press, Cambridge, 1996, 301.
34. K. Kannan and J. Falandysz, Mar. Pollut. Bull., 1997, 34, 203.
35. C. Alzieu, M. Heral, Y. Thibaud, M.J. Dardignac and M. Feuillet,
Rev. Trav. Inst. Marit., 1982, 45, 100.
36. C. Alzieu, Mar. Environ. Res., 1991, 32, 7.
37. C. Stewart and S.J. de Mora, Environ. Technol., 1990, 11, 565.
233 Chemistry of the Oceans
CHAPTER 5
The Chemistry of the Solid Earth
IAN D. PULFORD
Chemistry Department, University of Glasgow, Joseph Black Building,
Glasgow, G12 8QQ, UK
5.1 INTRODUCTION
Soil is the product formed when the rocks of the earth’s crust are
exposed at the surface and are subjected to various physical, chemical,
and, eventually, biological weathering processes. The minerals in these
rocks are predominantly silicates, which dominate the characteristics of
most soils. Table 1 shows those elements that are found in the crust
above an average concentration of 1% and their corresponding soil
content. The importance of aluminosilicates in soil is clear from the
enrichment factors of approximately 1 for O, Si, and Al. Some loss
occurs of K, Fe, Ca, Na, and Mg as a result of soil processes. But two
elements, C and N, show considerable enrichment in soil because of the
crucial role played by organic matter.
Table 1 Average elemental concentrations in the earth’s crust and in soil, and
the enrichment factor in soil
Element
Average concentration in crust
(%)
Average concentration in soil
(%)
Soil:crust
ratio
Oxygen 47 49 1.0
Silicon 28 31 1.1
Aluminium 8.2 7.2 0.88
Iron 4.1 2.6 0.63
Calcium 4.1 2.4 0.59
Magnesium 2.3 1.2 0.52
Sodium 2.3 1.2 0.52
Potassium 2.1 1.5 0.71
Carbon 0.05 2.5 50
Nitrogen 0.0025 0.20 80
Source: adapted from Sposito, The Chemistry of Soils, Oxford University Press, 1989.
234
Soil is formed not just by the weathering of minerals derived from rocks,
but also by the input of organic matter from the decomposition of plants
and, to a lesser extent, the decomposition and waste products of animals
and microorganisms. The relative amounts of the mineral and organic
components can vary widely, from almost all mineral materials, such as in
desert sand, to highly organic soil such as peat. It is the combination of the
mineral and organic components that gives soil its characteristics and
makes it a valuable resource, which can be used to grow crops for a number
of uses, such as food, fibre, and energy. These two aspects – soil develop-
ment and soil use – are reflected in two definitions of soil given by the Soil
Science Society of America (http://www.soils.org/sssagloss/):
The unconsolidated mineral or organic material on the immediate surface of
the earth that serves as a natural medium for the growth of land plants.
The unconsolidated mineral or organic material on the surface of the earth that
has been subjected to and shows the effects of genetic and environmental factors
of: climate (including water and temperature effects), and macro- and micro-
organisms, conditioned by relief, acting on parent material over a period of
time. A product – soil differs from the material from which it is derived in many
physical, chemical, biological, and morphological properties and characteristics.
The five points underlined in the second definition are known as the soil-
forming factors, which interact to produce a soil of particular characteristics
in any given place. The parent material is acted upon by a series of
weathering processes, outlined in Figure 1. Initially these are mainly
physical processes, which bring about a decrease in particle size, and hence
an increase in surface area. Weathering is strongly influenced by climate,
and, once living organisms colonize the developing soil, by biological
processes. Climate and relief interact to influence the movement of water
and weathering products through the soil. Most of these physical, chemical,
and biological processes proceed slowly, and so soil is evolving with time.
Soil is a combination of all of the major components of the surface
environment: the atmosphere, hydrosphere, lithosphere, and biosphere
(Figure 2). It is the mix and interaction of these four components that
result in the particular properties of a specific soil. The solid components
(mineral and organic matter) make up approximately 50% of soil by
volume. Air and water occupy the pore space between the solid phase,
and their relative amounts can vary considerably, resulting in important
effects on the chemical and biological processes in a soil. Various
measurements can be made to express the air–water balance in a soil
(Table 2).
235 The Chemistry of the Solid Earth
Exposed, unweathered parent material –
consolidated bedrock
or
unconsolidated material
(e.g. glacial drift; alluvium)
Physical weathering of parent material -
decrease of particle size, but little or no chemical alteration
Chemical / biological weathering of parent material –
formation of secondary minerals
Soil formation –
incorporation of organic matter into surface layers
soil forming processes in subsoil –weathering, leaching, etc.
slowly weathering parent material
Figure 1 Weathering sequence in soil
Soil
Atmosphere Biosphere
Lithosphere Hydrosphere
Soil air
Biomass
Humus
Rocks and
minerals
Soil water
Figure 2 Components of soil
236 Chapter 5
Worked example 5.1 – soil water and air contents, and bulk density
A soil core of 5 cm diameter and 8 cm height contains 257 g of fresh
soil. After drying the soil at 1101C, the soil weighed 196 g. Calculate
(i) the gravimetric soil water content, (ii) the volumetric soil water
content, (iii) the soil bulk density, (iv) the % pore space, (v) the %
water-filled pore space, and (vi) the % air-filled pore space.
Density of water ¼ 0.997 g cm
À3
Volume of soil core ¼ p.r
2
.h ¼ 3.14 Â (2.5)
2
 8 ¼ 157 cm
3
(i) Gravimetric soil water content ¼ [(257–196 g)/196 g] Â 100 ¼ 31%
(ii) Volumetric soil water content ¼ [(257–196 g)/(0.997 g cm
À3
 157
cm
3
)] Â 100 ¼ 39%
(iii) Soil bulk density ¼ 196 g/157 cm
3
¼ 1.25 g cm
À3
Assuming a soil particle density of 2.6 g cm
À3
, the volume of particles
in the soil core ¼ 196 g/2.6 g cm
À3
¼ 75.4 cm
3
(iv) % pore space ¼ [(157 cm
3
À75.4 cm
3
)/157 cm
3
] Â 100 ¼ 52%
(v) % water-filled pore space ¼ volumetric water content ¼ 39%
(vi) % air-filled pore space ¼ 52%À39% ¼ 13%
What is the weight of this soil in 1 ha to a depth of 20 cm?
1 ha ¼ 10,000 m
2
, therefore volume of soil to 20 cm ¼ 10,000 m
2
 0.2
m ¼ 2000 m
3
Bulk density of soil ¼ 1.25 g cm
À3
R1.25 t m
À3
2000 m
3
 1.25 t m
À3
¼ 2500 t of soil.
Table 2 Determination of soil water and air contents and bulk density
Gravimetric soil water content
(%)
(Mass of water/mass of oven dry soil) Â 100
Volumetric soil water content
(%)
(Volume of water/volume of soil core) Â 100
Soil bulk density (g cm
À3
) Mass of oven dry soil/volume of soil core
Soil particle-specific gravity (g
cm
À3
)
Mass of oven dry soil solids/volume of soil solids
Pore space (%) ((Soil core volume–volume of soil particles in
core)/soil core volume) Â 100
Solid material (%) (Volume of soil particles in core/total core
volume) Â 100
Water-filled pore space (%) Volumetric soil water content
Air-filled pore space (%) % pore space–% water-filled pore space
237 The Chemistry of the Solid Earth
5.2 MINERAL COMPONENTS OF SOIL
5.2.1 Inputs
The nature of the parent material is the most important factor influen-
cing the mineral components of a soil. In particular, the textural
(particle size) properties and inherent fertility are directly affected by
the types of rocks and minerals found in the parent material.
Parent material can be consolidated rock (igneous, sedimentary, or
metamorphic) or unconsolidated superficial deposits that have been
transported by some agency, such as wind, ice, or water. Igneous rocks
are formed from molten magma from the earth’s crust and are the
ultimate source of all rocks. Extruded igneous rock is formed when
molten magma appears at the surface and cools quickly, resulting in
small grain size (e.g. basalt). Intruded igneous rock cools slowly on its
way to the surface and results in large grain size (e.g. granite). Sedimen-
tary rocks are formed from the weathering products of igneous,
metamorphic, or older sedimentary rocks. Metamorphic rocks are
formed by changes in igneous or sedimentary rocks owing to high
temperature and/or high pressure, which usually has the effect of making
the rock more resistant to weathering. Unconsolidated materials are
surface deposits of partially weathered rock that have been transported
and deposited in various ways. The most important groups of such
materials, from which much of the world’s major soils are formed, are:
glacial deposits, resulting from the action of ice; alluvium, deposited
from water; and aeolian or wind-blown deposits.
w
5.2.2 Primary Minerals
The primary soil minerals, sometimes called ‘inherited’ minerals,
are those that are derived from the rocks of the parent material. They
are distinguished from the secondary, or ‘pedogenic’ minerals, which are
formed during the process of soil formation (see next section). The main
primary minerals are silicates (Table 3), all based on the SiO
4

tetrahedron, in which three oxygen atoms are in a triangular plane
below the silicon atom and one oxygen is above the silicon (Figure 3a).
There may be isomorphous substitution of silicon by aluminium. The
charge is balanced by cations such as K
1
, Na
1
, Ca
21
, Mg
21
, and Fe
21
.
The silica tetrahedra can be linked in a number of ways to form
silicates of differing structures, and hence susceptibility to weathering
w
A description of the origins and morphology of specific soil types is outwith the scope of this
chapter. An excellent description of the major soils of the world can be found at http://
soils.usda.gov/education/.
238 Chapter 5
(Figure 4). Quartz and the feldspars are framework silicates, in which
adjacent tetrahedra share all four oxygens. The micas form sheet silicates
by the sharing of three oxygens by each silica tetrahedron. The amphi-
boles and pyroxenes are chain silicates: amphiboles are double chains,
with the tetrahedra sharing two or three oxygens alternately; pyroxenes
are single chains with sharing of two oxygens. Olivine is an isolated
tetrahedon (or orthosilicate).
Table 3 Structures of common primary soil minerals
Quartz SiO
2
Feldspars
Microcline KAlSi
3
O
8
Albite NaAlSi
3
O
8
Anorthite CaAlSi
2
O
8
Micas
Muscovite KAl
2
(Si
3
Al)O
10
(OH)
2
Biotite K(Mg, Fe)
2
(Si
3
Al)O
10
(OH)
2
Amphiboles
Hornblende (Na, Ca)
2
(Mg, Fe, Al)
5
(Si, Al)
8
O
22
(OH)
2
Pyroxenes
Enstatite MgSiO
3
Augite Ca(Mg, Fe, Al)(Si, Al)
2
O
6
Olivine (Mg, Fe)
2
SiO
4
(a) (b)
Silicon Aluminium Oxygen or hydroxyl
Figure 3 Structure of (a) silica tetrahedron and (b) alumina octahedron
239 The Chemistry of the Solid Earth
In Table 3, susceptibility to weathering increases down the list as fewer
silicon–oxygen bonds need to be broken to release silicate. Conse-
quently, quartz and feldspars especially, but also mica in temperate
soils, are common inherited minerals in the coarse particle size fractions
of soil (the silt and sand fractions, 0.002–2 mm). The amphiboles,
pyroxenes, and olivine are much more easily weathered. Thus, soils
derived from parent material with rock containing a predominance of
framework silicates (e.g. granite, sandstone) tend to be more sandy,
while those derived from rocks containing the more easily weathered
minerals tend to be more clayey.
The chemical composition of the silicate minerals affects the inherent
nutrient properties of soil. Coming down the list of silicates in Table 3,
there is a change from the dominance of Si, Al, and Na in quartz and the
feldspars to greater contents of Ca, Mg, and Fe in the amphiboles,
pyroxenes, and olivine. These latter make up the so-called ‘ferromagne-
sian’ group of minerals, and soils in which they are an important
component of the parent material have better inherent nutrient proper-
ties. In particular, such soils are better buffered against the natural
acidification process that occurs due to loss of exchangeable cations,
especially Ca
21
and Mg
21
, by leaching (see Sections 5.4 and 5.5).
5.2.3 Secondary Minerals
Secondary minerals (which dominate the clay-size fraction of soil, o0.002
mm) are formed in soil by the action of various weathering processes on
(a) (b) (c) (d)
Figure 4 Structures of (a) ortho (isolated); (b) single chain; (c) double chain; and (d)
sheet silicates
240 Chapter 5
the primary minerals derived from the parent material (see section 5.2.4).
These may be formed by alteration of a primary mineral – e.g. the
conversion of mica into a clay mineral – or by reactions of soluble
products released into the soil environment – e.g. precipitation of iron
oxide. The most important groups of secondary minerals are: (a) the
aluminosilicate clay minerals; (b) short-range order (amorphous) alumi-
nosilicates; and (c) the hydrous oxides of Al, Fe, and Mn (Table 4).
In the study of soil science, most attention has historically been paid
to the aluminosilicate clays, which dominate the properties of temperate
soils, the first to be scientifically studied. More recently, the importance
of the amorphous aluminosilicates has been shown in young soils, in
soils derived from volcanic ash and in leached, acidic soil (e.g. podzols or
spodosols). The hydrous oxides are especially important components of
old, highly weathered soils, such as those found in the tropics (e.g.
oxisols). This is an important distinction as the charge on the alumino-
silicate clays is predominantly a permanent negative charge, while
the amorphous aluminosilicates and hydrous oxides have a variable,
Table 4 Structures of common secondary soil minerals
Clay minerals (phyllosilicates)
Kaolinite Al
4
Si
4
O
10
(OH)
8
Illite K
1.5
(Al
3.5
Mg
0.5
)(Si
7
Al)O
20
(OH)
4
Vermiculite M
0.7
Al
2
(Al
0.7
Si
3.3
)O
10
(OH)
2
M¼Ca
21
, Mg
21
, K
1
, etc.
Smectite M
0.3
Al
2
(Al
0.3
Si
3.7
)O
10
(OH)
2
M¼Ca
21
, Mg
21
, K
1
, etc.
Chlorite (Mg, Fe)
3
(Si, Al)
4
O
10
(OH)
2
(Mg, Fe)
3
(OH)
6
Amorphous aluminosilicates
Allophane xSiO
2
Á Al
2
O
3
Á yH
2
O (x¼0.8–2, y Z 2.5)
Imogolite SiO
2
.
Al
2
O
3
.
2.5H
2
O
Hydrous oxides
Goethite FeOOH
Haematite Fe
2
O
3
Ferrihydrite Fe
5
O
7
(OH)
.
4H
2
O
Gibbsite Al(OH)
3
Birnessite (Na, Ca)(Mn
31
, Mn
41
)
7
O
14
.
2.8H
2
O
Carbonates
Calcite CaCO
3
Dolomite CaMg(CO
3
)
2
Others
Gypsum CaSO
4
.
2H
2
O
241 The Chemistry of the Solid Earth
pH-dependent charge. This results in very different properties of tropical
soils compared to temperate soils.
5.2.3.1 Aluminosilicate Clay Minerals (Phyllosilicates). The alumi-
nosilicate clay minerals are sheet silicates. They are sometimes referred
to as phyllosilicates, but strictly this term should also include the micas,
which are primary minerals.
The basic building blocks of all the aluminosilicate clay minerals are
the silica tetrahedron (Figure 3a) and alumina octahedron (Figure 3b).
These build up into tetrahedral sheets by the sharing of oxygens between
adjacent silicons, and into octahedral sheets by the sharing of oxygens or
hydroxyls between adjacent aluminiums. The sharing of oxygens be-
tween tetrahedral and octahedral sheets leads to the formation of clay
unit layers, of which there are two basic types (Table 5): 1:1, one
tetrahedral Si sheet and one octahedral Al sheet, and 2:1, two tetra-
hedral Si sheets sandwiching one octahedral Al sheet.
Unit layers are held together in various ways to produce a clay crystal.
These are regular, rigid systems and the distance between equivalent
points in adjacent unit layers, the c spacing or basal spacing, can be
measured by X-ray diffraction and is used to identify the clay minerals
(Figure 5).
Within the sheets, Si or Al may be replaced by a different element by
the process of isomorphous substitution. Common replacements in the
clay minerals are Al
31
for Si
41
in the tetrahedral sheet and Mg
21
or
Fe
21
for Al
31
in the octahedral sheet. Substitution of an element by one
of a lower valency results in a deficit of positive charge, and hence the
development of a permanent negative charge on the clay mineral. In soils,
this charge is neutralized by cations in solution being attracted to the
negatively charged surface, and is called the cation-exchange capacity
Table 5 Components of soil clays and how they combine to form a clay mineral
Basic building
blocks
Si tetrahedra, Al octahedra
Sheets Tetrahedral sheet, made up of Si tetrahedra sharing oxygen atoms;
octahedral sheet, made up of Al octahedra sharing oxygens or
hydroxyls
Unit layers Sheets combined in the ratio of one tetrahedral:one octahedral (1:1), or
two tetrahedral:one octahedral (2:1)
Clay crystal Stacks of unit layers held together by various bonding mechanisms,
depending on the type of clay
242 Chapter 5
(CEC). This permanent negative charge is the major characteristic of
temperate soils, in which the aluminosilicate clays dominate the reactive
fraction. The consequences of this are discussed in relation to ion-
exchange processes in Section 5.5.
Kaolinite is the commonest 1:1 clay mineral. There is a small amount of
isomorphous substitution of Al for Si in the tetrahedral sheet, resulting in a
charge of r 0.005 mol negative charge per unit cell. The unit layers are
bound by hydrogen bonds between the oxygen atoms on the tetrahedral
face and the hydroxyls on the adjacent octahedral face, resulting in a low
CEC and surface area (Table 6) and a fixed c spacing of 0.7 nm. Unit
layers stack up to form hexagonal crystals typically 0.05–2 mm thick. This
means that the variable, pH-dependent charge on the clay edge is relatively
more important in kaolinite than the other aluminosilicate clays.
Illite (a hydrous mica) is a 2:1 clay mineral with isomorphous
substitution occurring mainly in the tetrahedral sheet (Al
31
for Si
41
),
although a small amount also occurs in the octahedral sheet (Mg
21
or
Fe
21
for Al
31
), resulting in a charge of 1.5 mol negative charge per unit
cell. Most of this charge is neutralized by K
1
ions in the interlayer space.
The geometrical arrangement of oxygen atoms on the tetrahedral face
allows the K
1
ions to sit very close to the clay surface, forming a very
strong bond between unit layers. This results in a low CEC and surface
area (Table 6) and a fixed c spacing of 1.0 nm.
Vermiculite, a 2:1 clay mineral, is also a hydrous mica, with isomor-
phous substitution in the tetrahedral sheet, resulting in a charge of
between 1.2 and 1.9 mol negative charge per unit cell. In this case the
interlayer space
2:1 unit layer
basal spacing or
c spacing
clay face
clay edge
Si tet. sheet
Si tet. sheet
Al oct. sheet
Figure 5 Structure of a 2:1 aluminosilicate clay mineral
243 The Chemistry of the Solid Earth
interlayer cations are mainly Mg
21
with some Ca
21
, which are more
strongly hydrated cations than K
1
(see Section 5.5). The water of
hydration associated with these cations widens the c spacing to 1.4
nm, and allows some degree of expansion.
Smectites are a group of 2:1 clay minerals that have a low degree of
isomorphous substitution and hence a low-layer charge. The commonest
smectite found in soil is montmorillonite, in which substitution occurs in
the octahedral layer giving 0.7 mol negative charge per unit cell. Because
the charge originates further from the clay surface, interlayer bonding is
weak, allowing expansion of the clay lattice and easy entry of cations and
water molecules into the interlayer space. Therefore, the CEC and surface
area are both high (Table 6). The c spacing is variable, up to 1.9 nm when
Ca
21
or Mg
21
are the dominant interlayer cations. If sodium is the
dominant cation, the smectites can be fully dispersed in suspension.
Chlorite is a 2:1:1 clay mineral, with the usual 2:1 unit layer of two
tetrahedral sheets and one octahedral held together by a sheet of brucite.
Brucite is a magnesium hydroxide in which about two thirds of the Mg
21
ions are substituted by Al
31
, resulting in a positive charge. This neutra-
lizes much of the negative charge that arises due to isomorphous
substitution in the tetrahedral sheets (2 mol negative charge per unit cell)
and forms a strong electrostatic bond between unit layers. There is also
hydrogen bonding between hydroxyls on the brucite sheet and oxygens on
adjacent tetrahedral sheets. As a result of this strong interlayer bonding,
the CEC and surface area are low, and the c spacing is fixed at 1.4 nm.
In reality, soil clays are often not so well defined. Interstratification is
common, with, for example, intergrades of vermiculite and illite or
smectite and illite being found. This means that some layers in the clay
Table 6 Properties of the common aluminosilicate clay minerals
Clay
mineral Type
CEC
(cmol
c
kg
À1
)
Surface
area
(m
2
g
À1
)
Expanding/
non-expanding
c spacing
nm
Interlayer
binding
Kaolinite 1:1 3–20 5–100 Non-
expanding
0.7 Hydrogen
bonds
Illite 2:1 10–40 100–200 Non-
expanding
1.0 K
1
ions
Vermiculite 2:1 80–150 300–500 Slight
expansion
1.4 K
1
, Ca
21
,
Mg
21
ions
Smectite 2:1 80–120 700–800 Fully
expanding
1.4–1.9 Interlayer
cations
Chlorite 2:1:1 10–40 300–500 Non-
expanding
1.4 Brucite sheet
and H
bonds
244 Chapter 5
mineral are illitic in nature, while others more closely resemble vermi-
culite or smectite. Weathering at the edges of the clay mineral can also
lead to changes. For example, at the edge of an illite crystal, there may
be some loss of interlayer K
1
ions and their replacement by other
cations. This results in a widening of the interlayer space to form the so-
called wedge site (Figure 6).
5.2.3.2 Short-Range Order (Amorphous) Aluminosilicates. This is a
group of minerals that have small particle size and no regular crystal
structure, and as a result produce poorly defined X-ray diffraction
patterns. They do, however, show some regular short-range structure.
Thus, there has been a tendency over recent years to describe them as
short-range order, rather than amorphous, aluminosilicates. They have
a very high surface area, making them highly reactive. They have both a
K
+
K
+
K
+
Mg
2+
Mg
2+
Mg
2+
H
2
O
H
2
O
H
2
O
H
2
O
Ca
2+
Ca
2+
Ca
2+
Kaolinite
Illite
Vermiculite
Smectite
Chlorite
Figure 6 Structures of common clay minerals Silica tetrahedral sheet; alumina
octahedral sheet; brucite sheet.
245 The Chemistry of the Solid Earth
fixed negative charge, arising from isomorphous substitution in Si
tetrahedral sheets, and a variable, pH-dependent charge similar to that
on clay edges and hydrous oxide surfaces. The two main minerals in this
group, allophane and imogolite, are found in young soils and soils of
volcanic origin.
5.2.3.3 Hydrous Oxides. This term is generally taken to include the
oxides, hydroxides, and oxyhydroxides of aluminium, iron and manga-
nese, which form in soil when these elements are released from primary
minerals by weathering. They exist mainly as small particles in the clay-
sized fraction of a soil (o2 mm), and also as coatings on other soil
minerals or as components of larger aggregates.
The most common aluminium oxide found in soil is gibbsite (gAl(OH)
3
),
which may be the final product resulting from the precipitation of
amorphous aluminium hydroxide. A number of iron oxides are found in
soil, the commonest being ferrihydrite, goethite, and haematite. Iron
released from weathering of the ferromagnesian minerals precipitates out
of solution as either ferrihydrite or goethite depending on soil conditions
(low organic matter and a high rate of Fe release favour ferrihydrite
formation). Ferrihydrite is a poorly ordered oxide of small particle size,
whereas goethite is a well-structured mineral and is the commonest of the
iron oxides. Haematite is derived by structural changes to ferrihydrite, and
is commonly found in tropical soils. Manganese oxides occur in a large
number of forms, often with variable valency, for example, birnessite, and
in mixed oxides, especially with iron. They are the least well understood of
this group of minerals.
The hydrous oxides have a variable, pH-dependent charge and are
important in soils as aggregating agents and as adsorptive surfaces (see
Section 5.5) (Figure 7).
5.2.4 Weathering Processes (See Also Chapter 3)
The processes that cause changes to the rocks and minerals of the soil
parent material are collectively known as weathering. In the early stages,
physical weathering dominates and results in fragmentation of rock, a
decrease in particle size, and increase in surface area, but no chemical
change. It is brought about by a number of actions:
Abrasion of the rock caused by the action of ice, water, and wind
leads to physical disintegration.
Temperature change due to diurnal temperature variation and by
freeze–thaw cycles can create significant pressures that will cause
rock to split along lines of weakness.
246 Chapter 5
Roots tend to grow into existing fissures and channels and can
exert significant pressure.
Crystallization of some salts can also cause swelling, which can
exert pressure.
The key factor about physical weathering is the increase in surface area
of rock that is then available for attack by various chemical-weathering
processes. Chemical weathering is the reaction with natural waters, and
dissolved components, resulting in partial or complete dissolution of the
rock and formation of a new mineral phase. In most cases, it is the
interaction of water with the minerals in the rock that is the crucial issue.
5.2.4.1 Dissolution. Some minerals, such as gypsum (CaSO
4
.2H
2
O),
are readily soluble in water and so can persist only in soils of arid and
semi-arid regions, where water is limiting. In temperate and tropical
regions sufficient water will pass through the soil to cause dissolution
and loss of gypsum:
CaSO
4
.2H
2
O !Ca
21
þ SO

4
þ 2H
2
O (5.1)
Quartz is a much less soluble mineral than gypsum, but even this is
slightly soluble:
SiO
2
þ 2H
2
O "H
4
SiO
4
(5.2)
This reaction is driven by the loss of the soluble silicic acid from the soil.
In temperate regions insufficient water passes through the soil, and
weathering has proceeded over a relatively short time since the last ice
Iron oxide surface below pzc
Overall positive charge
pzc = point of zero charge
pH at which net surface charge is zero
Iron oxide surface above pzc
Overall negative charge
Fe - OH
2
Fe - OH
2
O
+
O
Fe - OH
Fe - OH
2
O
0
O
Fe - OH
Fe - OH
O
-
O
Figure 7 Variable, pH-dependent charge on an iron oxide surface
247 The Chemistry of the Solid Earth
age, for there to have been significant loss of silica, and so quartz is a
dominant mineral in the coarse fraction of soils. In the humid tropics,
however, the much larger volume of water passing through the soil, over
a much longer timescale, has resulted in significant, if not complete, loss
of silica.
5.2.4.2 Acid Hydrolysis. The water that enters soil as rain or snow is
in equilibrium with CO
2
in the atmosphere, which dissolves to form
carbonic acid. Unpolluted rainwater has a pH of approximately 5.7,
whereas water in soil pores may be exposed to air containing a higher
partial pressure of CO
2
than the free atmosphere, and hence soil water
may be more acidic (see Section 5.4). It is the attack on soil minerals by
this weak carbonic acid that is the major chemical weathering process in
most soils. For example, acid hydrolysis of calcium carbonate yields
calcium and bicarbonate ions:
CaCO
3
þ H
2
CO
3
"Ca
21
þ 2HCO
À
3
(5.3)
Acid hydrolysis of the primary mineral microcline feldspar results in
release of some soluble components (silicic acid, potassium ions, and
bicarbonate ions) and alteration of the solid phase to kaolinite:
4KAlSi
3
O
8
þ 22H
2
O þ 4CO
2
"Al
4
Si
4
O
10
(OH)
8
þ 8H
4
SiO
4
þ 4K
1
þ 4HCO
À
3
(5.4)
5.2.4.3 Oxidation. For those elements that can exist in more than one
valence state oxidation, and indeed reduction, may be a major reaction
in the chemical-weathering process. Iron and manganese are the most
important elements that behave in this way. For example, iron in the
ferromagnesian minerals is in the Fe(II) state, which is oxidized to
Fe(III) when released from the mineral. This can cause changes in the
charge balance, requiring other ions to be lost. Formation of iron oxide
can cause physical disruption to the mineral.
5.2.4.4 Chelation. Once biological activity is established, an impor-
tant reaction is the formation of a stable complex between a metal ion
and an organic molecule due to release of organic compounds by
colonizing organisms and plant roots.
5.3 ORGANIC COMPONENTS OF SOIL
It cannot be emphasized enough that soil is formed by the interaction of
the mineral weathering product of rocks and the organic material
248 Chapter 5
introduced as a result of biological activity. Much of this organic material
is plant-derived litter and the amount added to soil per year depends very
much on the dominant vegetation type (Table 7). These figures do not
include inputs from roots, which may be significant but difficult to
quantify, or more resistant inputs, such as wood in forests. In addition,
animal and microbial excretion and decomposition must be taken into
account. The values in Table 7 do, however, give a reasonable estimate of
what may be described as degradable carbon entering soils per year.
The organic materials added to soil have varying degrees of suscept-
ibility to degradation. Simple compounds, such as sugars and amino
acids, are rapidly decomposed by soil microorganisms, whereas complex
material, such as lignin and hemicellulose, tends to persist in an unde-
graded or partially degraded form. About 70% of the carbon added to
soil is lost as carbon dioxide, produced mainly by microbial respiration.
The other 30% is incorporated into the microbial biomass and soil
humus, a resistant material, which degrades only very slowly. Figure 8
shows typical values for the annual turnover of organic matter in soil.
Humus formation proceeds broadly along two pathways (Figure 9).
Readily decomposed material releases low molecular weight com-
pounds, especially phenolic and amino compounds, which react and
polymerize to form humic material. Alternatively, the more resistant
organic material can undergo partial degradation, and this partially
degraded material may also react with the low molecular weight
compounds released into the soil, again leading to the formation of
humus. It is likely that both of these processes operate in soils.
The terms humus and humic substances are used interchangeably to
refer to the resistant organic material that persists in soil over relatively
long timescales (100s–1000s of years). Although the humic substances
may be chemically diverse, being dependent on the dominant type of
plant tissue input, they do have some overall similarities. They are
amorphous, colloidal polymers built up mainly from aromatic units.
There is a wide range of molecular weights, from 100s to 100,000s Da.
Table 7 Inputs of carbon to soil by various types of land use
Dominant land use Tonnes carbon added to soil ha
À1
year
À1
Alpine and arctic forest 0.1–0.4
Arable agriculture 1–2
Coniferous forest 1.5–3
Deciduous forest 1.5–4
Temperate grassland 2–4
Tropical rain forest 4–10
Source: adapted from White, Principles and Practice of Soil Science, Blackwell Science, 1997.
249 The Chemistry of the Solid Earth
All of these compounds do, however, have similar overall properties due
to the preponderance of carboxylic and phenolic functional groups on
the humic polymer. Both of these groups can ionize by losing a hydrogen
ion to give a negatively charged group. This is a variable charge, the
magnitude of which varies with pH, but is always negative and forms
part of the CEC of a soil (see Section 5.5).
R-COOH "R-COO
À
þ H
1
(5.5)
Input of plant
litter
4.0 t C ha
-1
(100%)
Lost from
soil as CO
2
2.8 t C ha
-1
(70%)
Incorporated
into new humus
1.2 t C ha
-1
(30%)
Reservoir of
C in soil
humus
72 t C ha
-1
Loss of CO
2
1.2 t C ha
-1
Figure 8 Typical annual turnover of organic matter in a temperate grassland soil at
steady state receiving 4 t C ha
À1
250 Chapter 5
OH O

+ H
+
ð5:6Þ
The pK of Equation (5.5) is in the range 3–5, and of Equation (5.6) in the
range 7–8. Thus, carboxyl groups are important in acid soils, while
phenolic groups become important above pH 7.
Input of plant residues
Attack by microorganisms
and soil fauna
Resistant material-
poorly degraded
Easily degraded
material
Partially
degraded
material
Loss of CO
2
, simple
inorganic ions (NO
3
-
etc.) and release of
simple organic
compounds, e.g. amino
acids, sugars and
polyphenols
Microbial activity
Reaction between
simple organic
compounds to form
more complex
polymers
Reaction of
simple
organics with
partially
degraded
material
Soil humic material
Figure 9 Possible pathways for formation of humic material in soil from inputs of plant
residues
251 The Chemistry of the Solid Earth
Soil organic matter has been traditionally fractionated into a number
of subgroups (Figure 10).
Humin and humic acid are high molecular weight fractions (410,000
Da) and it is thought that humin is not extracted by alkali because it is
too strongly bound to the soil mineral component. Fulvic acid is the low
molecular weight fraction (o10,000 Da). There are some chemical
differences between humic acid and fulvic acid, the latter being more
acidic and having a higher oxygen content and lower carbon content
than humic acid. This reflects the greater number of carboxylic and
phenolic groups in the fulvic acid fraction. It is speculated that humic
acid forms the less reactive backbone or core of the humic material,
while the more reactive fulvic acid is present as side chains branching
from the core.
Although there is considerable variation between soils, the ratio of the
major elements, C:N:P:S, in humic material is approximately 100:10:2:1,
forming a major reservoir of N, P, and S that is made available to
plants as soil organic matter, is broken down by soil micoorganisms.
Floatation
Sinks Floats
Extraction
with alkali
Insoluble Soluble
Acidify to pH1
Insoluble Soluble
Soil organic matter
Humic material Non-humic material
Humin
Humic colloids
Humic acid
Fulvic acid
Figure 10 Fractionation scheme for soil organic matter
252 Chapter 5
Identification of N-, P-, and S-containing compounds is difficult, and
those that are identified tend to be metabolic products, such as nucleo-
tides and vitamins, released into the soil following the death of cells.
Broadly, nitrogen is an integral part of the humic molecule, and is
released as NH
4
1
ions when the humic material is degraded. Phosphorus
and sulfur are more commonly found as P and S esters, which can be
released as orthophosphate and sulfate ions by the action of phospha-
tase and sulfatase enzymes, respectively.
Worked example 5.2 – organic carbon content of soil
Organic carbon in soil can be measured by oxidation with acid
dichromate solution:
2K
2
Cr
2
O
7
þ 3C þ 8H
2
SO
4
"2Cr
2
(SO
4
)
3
þ 3CO
2
þ 2K
2
SO
4
þ 8H
2
O
(5.7)
The excess dichromate is measured by titration with ferrous sulfate
Cr
2
O

7
þ 6Fe
21
þ 14H
1
"2Cr
31
þ 6Fe
31
þ 7H
2
O (5.8)
0.20 g soil was oxidized with 20 cm
3
of M/6K
2
CrO
7
in sulfuric acid.
The excess dichromate was determined by titration with 0.5 M FeSO
4
solution. A blank, no soil, control was carried out to assess loss of
dichromate by thermal decomposition. The titration values obtained
were 17.5 cm
3
for the soil sample and 39.0 cm
3
for the blank. What is
the % organic carbon in the soil?
Moles of Cr
2
O
7

added initially ¼ 20 Â 1/6 ¼ 3.334 mmol
Moles of Cr
2
O
7

remaining after reaction:
17.5 Â 0.5 ¼ 8.75 mmol Fe
21
From Equation (5.8), 1 mol of Cr
2
O
7

reacts with 6 mol of Fe
21
Therefore, 8.75/6 ¼ 1.458 mmol of Cr
2
O
7

unused.
Blank titration
39.0 Â 0.5 ¼ 19.5 mmol Fe
21
¼ 3.25 mmol of Cr
2
O
7

Therefore, 3.334–3.25 ¼ 0.084 mmol of Cr
2
O
7

lost by thermal
decomposition.
Moles of Cr
2
O
7

used in oxidation ¼ 3.334–1.458 ¼ 1.876 mmol
Subtract Cr
2
O
7

lost by thermal decomposition ¼ 1.876–0.084 ¼
1.792 mmol of Cr
2
O
7
2
From Equation (5.7) 2 mol of Cr
2
O
7

react with 3 mol of C
1.792 Â 3/2 ¼ 2.688 mmol C
2.688 Â 12 ¼ 32.26 mg carbon
(32.26 mg/200 mg) Â 100 ¼ 16.13% C in the soil.
253 The Chemistry of the Solid Earth
5.4 SOIL pH AND REDOX POTENTIAL
Soil pH, which is a measure of the acidity or alkalinity, and redox
potential, a measure of the aeration status, are the two crucial factors
that control many of the chemical and biological processes in soil.
5.4.1 pH and Buffering
pH is defined as Àlog[H
1
], i.e. the negative logarithm of the hydrogen
ion concentration (or strictly speaking its activity) in solution, and is
based on the concept of the partial ionization of water. In pure water,
the H
1
ion concentration is 10
À7
mol L
À1
and so the pH is 7. If the
concentration of H
1
ions increases, the pH falls below 7 (acid condi-
tions) and if the concentration decreases, the pH rises above 7 (alkaline
conditions). In soil, however, factors other than the H
1
ion concentra-
tion in solution affect the pH.
Measurement of pH in a soil is usually done using a glass pH electrode
in a soil suspension. It is important to state the ratio of the soil weight to
the solution volume used, because pH varies with dilution. Common
ratios are 1:1 (10 g:10 cm
3
), 1:2.5 (10 g:25 cm
3
), and 1:5 (10 g:50 cm
3
). It
is also necessary to state the nature of solution used, commonly
deionized water or a dilute salt solution (e.g. 0.01 M CaCl
2
). What is
actually being measured is the pH of a solution in equilibrium with
negatively charged soil particles – thus, some H
1
ions are in solution and
some on soil surfaces (see ion exchange, Section 5.5). The pH measured
depends on the ratio of these two pools of ions, and is affected by
dilution and the concentration of other ions in solution. If care is taken
in measuring pH, it is a very useful parameter from which a lot can be
deduced about a soil. However, it must be borne in mind that in the field
soil pH can vary significantly over short distances and over relatively
short timescales.
H
1
and Al
31
ions in solution and on surface-exchange sites constitute
the solution and exchangeable acidity in a soil, also called the active
acidity. The non-exchangeable, or reserve, acidity is associated with
carboyxl and phenolic groups on humic material, OH groups on
hydrous oxide surfaces and clay edges, and polymeric aluminium
hydroxides. The balance between solution and exchangeable acidity
and non-exchangeable acidity can shift in response to a change in pH:
Non-exchangeable acidity "Exchangeable and solution acidity (5.9)
If soil pH is increased (H
1
in solution decreased), the equilibrium shifts
to the right – some non-exchangeable acidity released. If soil pH is
254 Chapter 5
decreased (H
1
in solution increased), the equilibrium shifts to left –
some acidity goes on to non-exchangeable acidity. This represents the
buffer capacity of a soil, and acts to avoid large changes in pH. Acidity in
soil is normally corrected by addition of a liming material such as
CaCO
3
. The amount required can be calculated by measuring the
buffering of a soil by titration with a dilute solution of an alkali (often
Ca(OH)
2
is used). The amount of alkali needed to reach the required pH
can be found from the buffer curve.
Worked example 5.3 – soil buffering and liming
To raise the pH of 5 g of the soil in Worked example 5.1 to 6.5,
required addition of 4 cm
3
of 0.005 mol L
À1
Ca(OH)
2
solution. How
much calcium carbonate would be required to be added to 1 ha? (Mol
wt CaCO
3
¼ 100).
4 cm
3
of 0:005 mol L
À1
¼ 0:02 mmol CaðOHÞ
2
solutionfor 5 g soil
¼ 0:004 mmol g
À1
¼ 0:4 mg CaCO
3
g
À1
ð1 mmol CaCO
3
¼ 100 mgÞ
¼ 0:4 kg CaCO
3
t
À1
From Worked example 5.1, there are 2500 t ha
À1
in the top 20 cm,
which approximates to rooting depth.
0.4 kg CaCO
3
t
À1
 2500 t ¼ 1000 kg CaCO
3
required ha
À1
.
5.4.2 Soil Acidity
The atmosphere is a major source of soil acidity. Even in unpolluted
environments rainwater is slightly acidic, having a pH of about 5.7 due
to the dissolution of atmospheric CO
2
to form the weak carbonic acid
(see Worked example 5.4). The CO
2
concentration in the partially
enclosed soil pore system can be significantly higher (typically up to
about 10 times) than in the free atmosphere due to respiration of soil
microorganisms and plant roots. This results in a lower pH. In areas
affected by industrial pollution, sulfur dioxide and nitrogen oxides
dissolve in rainwater to produce sulfuric and nitric acids (acid rain),
which are both strong acids and cause even more acidity.
255 The Chemistry of the Solid Earth
Worked example 5.4 – pH of soil solution
Carbon dioxide dissolves in water to form carbonic acid, which is a
weak acid.
CO
2
þ H
2
O "H
2
CO
3
K ¼ 10
À1.5
(5.10)
[H
2
CO
3
]/pCO
2
¼ 10
À1.5
mol L
À1
atm
À1
Carbonic acid dissociates to produce bicarbonate and hydrogen ions
H
2
CO
3
"HCO
3
À
þ H
1
K ¼ 10
À6.4
(5.11)
½HCO
À
3
Š½H
þ
Š
½H
2
CO
3
Š
¼ 10
À6:4
mol L
À1
½HCO
À
3
Š ¼ ½H
þ
Š
½H
þ
Š
2
¼ 10
À6:4
½H
2
CO
3
Š ¼ 10
À6:4
 10
À1:5
 pCO
2
pCO
2
in the atmosphere ¼ 10
À3.5
atm
½H
þ
Š
2
¼10
À6:4
mol L
À1
 10
À1:5
mol L
À1
atm
À1
 10
À3:5
atm ¼ 10
À11:4
½H
þ
Š ¼10
À5:7
mol L
À1
pH ¼5:7
If the partial pressure of CO
2
in the soil atmosphere is considered to
be 10 times greater than the free atmosphere,
½H
þ
Š
2
¼10
À6:4
mol L
À1
 10
À1:5
mol L
À1
atm
À1
 10
À2:5
atm ¼ 10
À10:4
½H
þ
Š ¼10
À5:2
mol L
À1
pH ¼5:2
Sulfur dioxide dissolves to form the strong acid, sulfurous acid, so is
strongly acidifying at very low concentrations. For example, for pSO
2
¼ 10
À7
atm (a value much higher than concentrations now occurring
owing to air pollution control measures in developed countries. Note,
however, that low-pH rainfall still occurs as a result of incorporation
of sulfuric and nitric acids).
SO
2
þ H
2
O "H
2
SO
3
K ¼ 1 (5.12)
[H
2
SO
3
]/pSO
2
¼ 1 mol L
À1
atm
À1
256 Chapter 5
H
2
SO
3
"HSO
À
3
þ H
1
K ¼ 1.7 Â 10
À2
(5.13)
½HSO
À
3
Š½H
þ
Š
½H
2
SO
3
Š
¼ 1:7 Â 10
À2
mol L
À1
½H
þ
Š
2
¼1:7 Â 10
À2
mol L
À1
 1mol L
À1
atm
À1
 10
À7
atm ¼ 1:7 Â 10
À9
½H
þ
Š ¼4:12  10
À5
log½H
þ
Š ¼ À 4:4
pH ¼4:4
Various soil processes also contribute to soil acidity. Decaying organic
matter releases a number of organic acids, as indeed do plant roots.
Nitrification, the microbial oxidation of ammonium ions to nitrate by
Nitrosomonas and Nitrobacter, occurs in slightly acidic to neutral soils
and releases H
1
ions:
2NH
þ
4
þ 3O
2
-2NO
À
2
þ 4H
1
þ 2H
2
O (5.14)
2NO
À
2
þ O
2
-2NO
À
3
(5.15)
Sulfide oxidation, another microbially mediated process, also results in
the production of acidity:
2FeS
2
þ 2H
2
O þ 7O
2
"2FeSO
4
þ 2H
2
SO
4
(5.16)
4FeSO
4
þ 10H
2
O þ O
2
"4Fe(OH)
3
þ 4H
2
SO
4
(5.17)
Note that in this case much of the acidity is due to the precipitation of
iron(III) oxide.
Leaching, the passage of water through the soil profile, is a process
that occurs in soils in areas of moderate to high rainfall, and which
results in the loss of exchangeable cations (such as Ca
21
, Mg
21
, K
1
, and
Na
1
– see Section 5.5). Unless the rate of weathering of soil minerals is
sufficiently rapid to replace these losses, the exchange sites will become
occupied by H
1
and Al
31
, which are acidic cations.
5.4.3 Soil Alkalinity (see also Section 3.2.4)
Alkaline soils (pH 4 7) contain solid phase carbonate, and bicarbonate
is the dominant anion in solution. Calcium and magnesium carbonates
257 The Chemistry of the Solid Earth
produce a soil of pH between 7 and 8.5, depending upon the concentra-
tions of CO
2
and Ca
21
or Mg
21
ions. In arid regions, the lack of rainfall,
and hence leaching, allows the more soluble Na
2
CO
3
to accumulate and
the pH rises to about 10.5.
5.4.4 Influence of pH on Soils
A major influence of pH on soil is its effect on biological activity. Many of
the soil microorganisms function within a narrow optimal range of pH
and their activity is inhibited in more acidic or alkaline conditions. For
example, the nitrifying bacteria mentioned above, Nitrosomonas and
Nitrobacter, have a pH optimum in the range 6–8, and are severely
inhibited below pH 5.5. Conversely, the iron- and sulfur-oxidizing
bacteria of the genus Thiobacillus are active only under acid conditions,
and are inhibited at pH 4 5. In general, bacteria are less tolerant of acid
conditions than fungi. Soil animals too are affected by pH; earthworms,
for example, cannot survive below a pH of about 4.5.
Certain soil components have a variable, pH-dependent charge. The
charge on the humified soil organic matter is negative overall due to
dissociation of carboxyl and phenolic groups, but its magnitude varies,
being greater at high pH (see Section 5.3). The hydrous oxides and edges
of clay minerals are positively charged at low-pH values and negative at
P
Ca, Mg
N, S
Mn, Fe, Cu, Zn
pH
4.0
8.0
R
e
l
a
t
i
v
e

a
v
a
i
l
a
b
i
l
i
t
y

o
f

n
u
t
r
i
e
n
t
Figure 11 Relative availabilities of plant nutrients in soil as affected by pH (only relative
amounts of individual nutrients should be compared)
258 Chapter 5
high pH (see Section 5.2). In general, therefore, low pH results in a
lessening of the negative charge on the surfaces of soil particles.
pH has a big influence on the solubility of many important elements in
soil, and can have a big influence on the availability of plant nutrients
(Figure 11). Aluminium, which is not required by plants, is relatively
insoluble except under acid conditions when toxicity problems may
occur. Using gibbsite, Al(OH)
3
, which is a common Al mineral in many
soils, as an example, the effect of pH on the concentration of aluminium
in solution can be modelled.
Worked example 5.5 – effect of pH on concentration of aluminium in
soil solution
What is the concentration of Al
31
ions in soil solution at the pH
values calculated in Worked example 5.4 for soil solution at (a) pCO
2
¼ 10
À2.5
atm and (b) pSO
2
¼ 10
À7
atm?
Using the dissolution of gibbsite as a model,
Al(OH)
3
"Al
31
þ 3OH
À
Solubility product,
K
SP
¼ 5 Â 10
À33
(5.18)
½Al
3 þ
Š½OH
À
Š
3
¼ 5 Â 10
À33
ðaÞ At pCO
2
¼ 10
À2:5
atm
pH ¼ 5:2; pOH ¼ 8:8
½OH
À
Š ¼1:58  10
À9
½OH
À
Š
3
¼3:94 Â 10
À27
½Al
3 þ
Š ¼ð5  10
À33
Þ=ð3:94 Â 10
À27
Þ
¼1:27 Â 10
À6
mol L
À1
ðbÞ At pSO
2
¼ 10
À7
atm
pH ¼ 4:4; pOH ¼ 9:6
½OH
À
Š ¼2:51  10
À10
½OH
À
Š
3
¼1:58 Â 10
À29
½Al
3 þ
Š ¼ð5  10
À33
Þ=ð1:58 Â 10
À29
Þ
¼3:2 Â 10
À4
mol L
À1
:
259 The Chemistry of the Solid Earth
5.4.5 Redox Potential
Redox potential is the measure of the oxidation–reduction state of a soil,
and is determined by redox reactions involving the transfer of electrons
from one chemical species to another. A generalized redox reaction can
be written as
Ox þ mH
1
þ ne
À
"Red (5.19)
where ‘Ox’ and ‘Red’ are the oxidized and reduced species, respectively.
Note also that H
1
ions are involved in the reaction, and so pH affects
the redox potential.
The potential produced is a consequence of the ratio of oxidized to
reduced species, and is expressed by the Nernst equation
E ¼E
0
À
RT
nF
ln
½RedŠ
½OxŠ
ð5:20Þ
where
E ¼ potential in volts
E
0
¼ standard electrode potential
R ¼ universal gas constant (8.314 J mol
À1
K
À1
)
T ¼ absolute temperature in K
n ¼ number of electrons involved
F ¼ Faraday constant 96,487 C mol
À1
(the charge when 1 mole of [Ox] is
reduced).
If a temperature of 251C (298 K) is assumed, the values of the
constants R and F are used and natural logs converted to log
10
, the
equation becomes
E ¼E
0
À
0:0591
n
log
10
½RedŠ
Ox ½ Š
ð5:21Þ
Redox potential is measured using an inert platinum electrode, which
acquires the electric potential (E
H
) of the soil when placed into the soil
or a soil suspension. This potential is measured relative to a reference
electrode with a known potential, such as the calomel electrode (E
cal
),
which has a potential of 0.248 V at 251C. This potential has to be added
to the measured value
E
H
¼ E
cal
þ 0.248 V (5.22)
260 Chapter 5
E
H
is measured at the pH of the sample, but is often expressed corrected
to pH 7 by subtracting 0.0591 V per unit pH up to 7 for samples with a
pH below 7 and adding 0.0591 V per unit pH down to 7 for samples
above pH 7.
E
H
can also be expressed as pe, which is the negative log of the electron
activity (analogous with pH) (see also Chapter 3). This approach considers
electrons as a reactant or product in the reaction. The two are related by
E
H
(in volts) ¼ 0.0591 pe (5.23)
Worked example 5.6 – redox limits in aqueous systems (see also Section
3.2.4.2)
The limits of redox potential in aqueous systems are determined by
the oxidation or reduction of water.
Oxidation of water
2H
2
O "O
2
þ 4H
1
þ 4e
À
log K ¼ À83.1 (5.24)
logK ¼ log pO
2
þ 4log H
þ
þ 4log e
À
À83:1 ¼ log pO
2
þ 4logH
þ
þ 4loge
À
83:1 ¼ Àlog pO
2
þ 4pH þ 4pe
For pO
2
¼ 1atm; log pO
2
¼ 0
83:1 ¼ 4pH þ 4pe
pe ¼ 20:78 À pH
Reduction of water
2H
1
þ 2e
À
"H
2
log K ¼ 0 (5.25)
pK ¼ ÀlogpH
2
À 2pH À 2pe
For pH
2
¼ 1atm; logpH
2
¼ 0
pe ¼ ÀpH
At pH 7, this gives theoretical limits for the soil environment at E
H
¼
approximately þ0.8 V (oxidizing) and approximately À0.4 V (reducing).
In practice soil atmospheres will not contain 1atmof oxygen or hydrogen.
5.4.6 Reduction Processes in Soil
Reduction is caused by a decrease in oxygen concentration in the soil
atmosphere; for example, by waterlogging or compaction. Oxygen
261 The Chemistry of the Solid Earth
diffuses through water 10
4
times more slowly than through air, and so
oxygen concentration falls. The microbial population changes in re-
sponse to the decreased oxygen, from aerobic organisms, requiring
oxygen for respiration, to facultative anaerobes, which can use sources
of electrons other than oxygen, to obligate anaerobes, which cannot
survive if oxygen is present. As the microbial population changes, their
use of alternative electron sources to oxygen causes a series of important
redox changes in soil (Table 8).
As each of these reduction processes occurs, the E
H
is buffered, or
poised, at a particular value. So, for example, while there is nitrate
present, the system will be poised at around þ0.22 V; once the nitrate
has been used up, reduction of Mn
IV
will poise the system at around
þ0.2 V, and so on. E
H
in oxidized systems is difficult to measure because
there is not a specific reaction controlling it. Generally, when oxygen is
present, the E
H
is greater than þ0.3 V.
The phase changes that occur are important: the gaseous products can
be lost from the soil to the atmosphere; Mn and Fe become soluble and
can be moved within or out of the system.
Reduction of NO
3
À
, Mn
IV
, and Fe
III
can occur under moderately
reduced conditions, such as intermittently waterlogged soil or sediment.
Reduction of nitrate causes the loss of a major nutrient. Often the
reduction does not proceed through to the formation of N
2
gas, and
nitrous oxide (N
2
O) is formed, which is a potent greenhouse gas and can
Table 8 Redox reactions in soil
Redox reaction Range of soil E
H
values (V)
O
2
þ 4H
þ
þ 4e
À
Ð 2H
2
O Disappearance of oxygen
0.6–0.4
2NO
À
3
þ 12H
þ
þ 10e
À
Ð N
2
þ 6H
2
O
solution gas
Disappearance of nitrate
0.5–0.22
MnO
2
þ 4H
þ
þ 2e
À
Ð Mn

þ 2H
2
O
solid solution
Appearance of Mn
II
0.4–0.2
FeðOHÞ
3
þ 3H
þ
þ e
À
Ð Fe

þ 3H
2
O
solid solution
Appearance of Fe
II
0.3–0.1
SO

4
þ 10H
þ
þ 8e
À
Ð H
2
S þ 4H
2
O
solution gas
Disappearance of sulfate
0 to À0.15
CO
2
þ 8H
þ
þ 8e
À
Ð CH
4
þ 2H
2
O
gas gas
Appearance of methane
À0.15 to À0.22
Source: adapted from Bohn, McNeal and O’Connor, Soil Chemistry, Wiley Interscience, 1985.
262 Chapter 5
cause ozone depletion in the atmosphere. Redox changes of Mn and Fe
are the main factor in the formation of gleys (waterlogged soils). Re-
oxidation to Mn
IV
and Fe
III
results in precipitation of highly reactive
oxides, which can sorb significant amounts of anions such as phosphate
and heavy metals. Sulfide and methane production occur only under
highly reduced conditions, such as permanently waterlogged and peat
soils. Sulfide may be lost as hydrogen sulfide gas, but often metals
sulfides (e.g. iron sulfide (FeS)) are precipitated. Methane is a potent
greenhouse gas.
5.5 CHEMICAL REACTIONS IN SOIL
Two of the important chemical functions of a soil are:
(i) to supply nutrients to plants and
(ii) to act as a filter or sink for pollutants.
In both cases, the crucial chemistry governing the process occurs at
the interface between soil solution and the solid phase. Various mechan-
isms control the equilibrium between chemical species in the two phases,
with movement between them being controlled by changes in solution
concentration.
5.5.1 Reactions in Soil Solution
The soil solution contains dissolved gases (carbon dioxide being parti-
cularly important – see Section 5.4), soluble organic molecules from soil
organic matter or exuded by plants and microorganisms, and inorganic
ions released from minerals by weathering or, in agricultural soils, added
as fertilizer. Typical ranges of ionic concentrations are given in Table 9.
Inorganic ions can exist as hydrated ions in solution, with the form of
the ion being determined by its charge (z) and size (r), expressed as the
ionic potential z
2
/r. Ions with a small ionic potential (oapproximately
six) are present in solution as the hydrated ion (e.g. in soil solution, K
1
Table 9 Typical ionic concentrations in soil solution at pH 6–7
Ions Concentration range
Ca
21
, NO
3
À
10
À2
–10
À3
mol L
À1
Mg
21
, K
1
, Na
1
, Cl
À
, HCO
3
À
10
À3
–10
À4
mol L
À1
H
2
PO
4
À
10
À5
–10
À6
mol L
À1
Trace elements (Zn, Cu, etc.) o10
À6
mol L
À1
263 The Chemistry of the Solid Earth
and Na
1
are weakly hydrated cations, while Ca
21
and Mg
21
are
strongly hydrated). Ions with a medium ionic potential (10–20) tend
to hydrolyze and precipitate as oxides and hydroxides (e.g. Fe
III
, Al
III
,
Cr
III
). Those with a high-ionic potential (420) form soluble oxyanions
(e.g. phosphate, nitrate, sulfate).
The chemical speciation of the ions is highly dependent on pH and redox
potential. Phosphorus, for example, exists as orthophosphate anions:
H
3
PO
4
"H
2
PO
À
4
þ H
1
pK 2.15 (5.26)
H
2
PO
À
4
"HPO

4
þ H
1
pK 7.20 (5.27)
HPO

4
"PO

4
þ H
1
pK 12.35 (5.28)
Over the pH range of most soils, the dominant orthophosphate anion in
soil solution will be H
2
PO
4
À
(Figure 12). Only in alkaline soils will
HPO
4

be significant, and PO
4

ions are not important in soil
solution.
Interactions between ions in solution can be considered in two ways.
Long-range interactions, those 40.5 nm, are accounted for by the
Figure 12 A distribution diagram showing the percentage composition of phosphoric acid
specified as a function of pH
(Reproduced from Harrison, R.M. et al., Introductory Chemistry for the
Environmental Sciences, Cambridge University Press, Cambridge, 1991.)
264 Chapter 5
concept of ion activity (see also Chapter 3)
{i} ¼ g
i
[i] (5.29)
where
{i} ¼ activity of the ion
[i] ¼ concentration of ion (mol L
À1
)
g
i
¼ activity coefficient.
At infinite dilution, {i} ¼ [i], i.e. g
i
¼ 1. Ionic interaction increases with
concentration and the square of the ionic charge, which is described by
the ionic strength of the solution (I):
I ¼
1
2
X
½iŠ z
2
i
ð5:30Þ
where
I ¼ ionic strength
[i] ¼ molarity of each ion in soilution
z
i
¼ charge on each ion in solution.
If all the ions in soil solution can be accounted for, I can be calculated,
and then g.
The relationship between the activity coefficient of an ion and the ionic
strength of the solution is given by the Debye–Hu¨ ckel limiting law
Log
10
g
i
¼ À0:5 z
2
i
ffiffiffi
I
p
ð5:31Þ
For soil solutions, the Davies equation, which is a modification of the
Debye–Hu¨ ckel equation, is commonly used, and is applicable to solu-
tions up to approximately I ¼ 0.7 mol L
À1
(see also Section 3.2.1):
Log
10
g
i
¼ À0:5 z
2
i
ffiffiffi
I
p
= 1 þ
ffiffiffi
I
p

À 0:3I
h i
ð5:32Þ
Worked example 5.7 – soil solution chemistry: ionic strength and
activity coefficients
The following analytical data were obtained for an isolated soil
solution:
Ca
21
, 5.05 mmol L
À1
; Mg
21
, 3.55 mmol L
À1
; K
1
, 0.68 mmol L
À1
;
Na
1
, 1.80 mmol L
À1
; NO
3
À
, 3.70 mmol L
À1
; HCO
3
À
, 1.80 mmol L
À1
;
SO
4

, 6.25 mmol L
À1
; and Cl
À
, 1.40 mmol L
À1
.
265 The Chemistry of the Solid Earth
How can we tell from these figures that the main ionic species have
been accounted for?
There are 19.68 mmol L
À1
of monovalent positive charge and 19.40
mmol L
À1
of monovalent negative charge.
What is the ionic strength of this solution?
I ¼1=2½ð5:05  2
2
Þ þ ð3:55 Â 2
2
Þ þ ð0:68 Â 1
2
Þ þ ð1:80 Â 1
2
Þ
þ ð3:70 Â 1
2
Þ þ ð1:80 Â 1
2
Þ þ ð6:25 Â 2
2
Þ þ ð1:40 Â 1
2
ފ
¼1=2 Â 68:78
¼34:39 in terms of concentrations in mmol L
À1
Ionic strength is expressed in terms of mol L
À1
I ¼ 0.0344.
What is the activity coefficient of each ion?
By substituting I ¼ 0.0344 into the Davies equation,
g monovalent ions ¼ 0.843,
g divalent ions¼0.504.
Short-range (o0.5 nm) interactions between ions in solution result in
the formation of ion pairs or complexes with other ions or with organic
molecules. An ion pair is a transient entity formed by coulombic
attraction between ions of opposite charge, with each ion retaining its
own water of hydration. In a complex, the ions form covalent or
coordinate bonds to form an entity with its own hydration shell.
An example of an ion pair could be between calcium and sulfate ions
in solution:
Ca
21
þ SO

4
"CaSO
0
4
(5.33)
An example of a complex could be between copper ions and an organic
molecule:
COOH
COO
OM
+ Cu
2+
OM Cu
COOH
COO
(5.34)
266 Chapter 5
Worked example 5.8 – activity of ions pairs in soil solution
In a soil solution the activity of Ca
21
¼ 10
À3
mol L
À1
and SO
4

ions
¼ 5 Â 10
À4
mol L
À1
, what is the activity of the ion pair CaSO
4
0
?
CaSO
0
4
"Ca
21
þ SO

4
K ¼ 5.25 Â 10
À3
(5.35)
½Ca
2 þ
Š½SO

4
Š
½CaSO
0
4
Š
¼ 5:25 Â 10
À3
½CaSO
4
Š ¼
ð10
À3
Þð5 Â 10
À4
Þ
5:25 Â 10
À3
¼ 9:5 Â 10
À5
mol L
À1
Alternatively, this calculation can be done using logarithms.
CaSO
0
4
"Ca
21
þ SO

4
log K¼ À2.28 (5.36)
log½CaSO
4
Š ¼log½Ca
2 þ
Š þ log½SO

4
Š À ð À 2:28Þ
¼ð À 3:00Þ þ ð À 3:30Þ À ð À 2:28Þ ¼ À4:02
½CaSO
4
Š ¼9:5  10
À5
mol L
À1
5.5.2 Ion Exchange (Physisorption)
Ion exchange is the process where ions held at a charged surface by
coulombic bonding are exchangeable with other ions of the same charge
in solution in contact with the surface. The reaction of major importance
in soils is cation exchange – i.e. positively charged ions (cations) held at
negatively charged surfaces. Anion exchange can occur, but is of minor
importance.
The solid phase surfaces on which cation exchange occurs are:
Silicate clays permanent negative charge on clay faces
pH-dependent charge on clay edges
Humified organic matter pH-dependent charge
(always overall negative)
Hydrous oxides pH-dependent charge
(overall positive or negative)
267 The Chemistry of the Solid Earth
The strength of the attractive force between the cation in solution and
the negatively charged surface of the soil component is governed by
Coulomb’s law:
F ¼
q
0
:q
00
ðconstantÞ
D:r
2
ð5:37Þ
Where
F is the attractive (or repulsive) force
q
0
and q
00
are the charges on the ion and the surface
D the dielectric constant and
r the distance of separation between the two charges.
Thus, more highly charged ions are held at exchange surfaces in
preference to lesser charged ions. Trivalent ions such as Al
31
and Fe
31
are most strongly held, then divalent ions such as Ca
21
and Mg
21
, with
monovalent ions being the least strongly held. For ions of the same
charge, the strength of binding depends on the size of the hydrated ion,
which is the species that exists in soil solution, and hence how close to
the surface it can approach. So for monovalent ions, the relative
strength of binding, or affinity for the surface, is Cs
1
4 Rb
1
4 K
1
4 Na
1
4 Li
1
. Ionic concentration must also be taken into account, as
these preferences can be overcome by high concentrations of an ion in
soil solution. For example, sodium ions would dominate the exchange
sites in soil flooded by seawater.
Ions are considered to be held at the charged surface in a diffuse double
layer (the Guoy–Chapman model) in which the concentration of cations
falls, and that of anions increases, with distance from the surface. In a
refinement of this, the Stern model introduces a layer of cations held
directly on the surface of the soil component (Figure 13). Small cations,
or dehydrated ions having lost their water of hydration, can sit at the
surface and form a strong coulombic bond. This allows for the speci-
ficity described above.
The exchange process can be written as a chemical reaction, so, for
example, for K
1
ions in soil solution exchanging with Ca
21
on the
surface (X)
CaX þ K
þ
Ð KX þ
1
2
Ca
2 þ
ð5:38Þ
At equilibrium, the ratio of the ions on the surface is related to their
ratio in solution:
KX
CaX
¼ k:
ðK
þ
Þ
ffiffiffiffiffiffi
Ca
p

ð5:39Þ
268 Chapter 5
The exchange is between equivalents of charge. Strictly, ionic activity,
not concentration, should be considered, but as ionic concentration in
soil solution is so low, it is commonly used. This is known as the Gapon
equation. This approach stresses the importance of the ion activity
ratio, which tends to remain constant. As a result, monovalent ions
are lost from a soil by leaching in preference to divalent and tri-
valent ions. A consequence is the acidifcation of soil by leaching (see
Section 5.4).
5.5.2.1 Cation-Exchange Capacity (See Also Chapter 4). The CEC of
a soil is a measure of its ability to hold cations at negative sites by
coulombic bonds. Because the exchange is by equivalents of charge, the
units used for CEC are centimoles of monovalent charge per kilogram of
soil (cmol
c
kg
À1
). (Previously the units of milliequivalents per 100 g
soil were used (meq 100 g
À1
); the numerical value of CEC is the
same whether expressed as cmol
c
kg
À1
or meq 100 g
À1
.) Typical values
of CEC for the aluminosilicate clays given in Section 5.2 are shown
in Table 6. These values for clay minerals are accounted for mainly by
the permanent negative charge formed owing to isomorphous substitu-
tion, with only a minor component coming from the variable, pH-
dependent charge on the clay edge. Humified organic matter has a
CEC typically between 150 and 300 as cmol
c
kg
À1
, all of which is
pH dependent; the hydrous oxides also have a pH-dependent charge,
M
n+
A
n-
M
n+
M
n+
M
n+
M
n+
M
n+
A
n-
M
n+
M
n+
A
n-
M
n+
M
n+
A
n-
M
n+
M
n+
M
n+
M
n+
M
n+
A
n-
A
n-
M
n+
M
n+
M
n+
M
n+
Negative Stern Diffuse layer Free solution
Surface layer cations > anions cations = anions
Figure 13 The distribution of ions at a negatively charged surface of a soil component
269 The Chemistry of the Solid Earth
but at most soil pHs the negative charge contributing to the CEC is
small.
In a soil of between pH 6 and 7, about 80% of the cation-exchange
sites hold Ca
21
, about 15% Mg
21
, K
1
, and Na
1
account for up to 5%,
with small amounts of NH
4
1
and H
1
. As the pH falls, Al
31
, Mn
21
, and
H
1
become relatively more important.
The % base saturation is a measure of the amount of the CEC of a soil
holding the major cations (also called exchangeable bases) Ca
21
, Mg
21
,
K
1
, and Na
1
.
% base saturation ¼
P
Ca
2 þ
; Mg
2 þ
; K
þ
; Na
þ
CEC
 100 ð5:40Þ
where the units of exchangeable cations and CEC are cmol
c
kg
À1
.
% base saturation is high (approximately 80%) in fertile soils with
basic minerals in the parent material and low (o30%) in highly leached
acidic soils.
Worked example 5.9 – cation-exchange capacity and % base saturation
One method to measure the CEC of a soil is to leach a column
containing a known weight of soil with a solution of a salt so that the
exchange sites are saturated with the cation (index ion). After washing
out the excess salt solution, a different salt solution is leached through
the column and the exchangeable ions displaced, collected in a known
volume and their concentration measured.
10 g soil was leached with 200 cm
3
of 1 mol L
À1
CH
3
COOK solution
in order to saturate the exchange sites with K
1
ions. After washing
out the excess CH
3
COOK solution, 200 cm
3
of 1 mol L
À1
CH
3
COONH
4
solution was passed through to displace the K
1
ions
by NH
4
1
. The solution that leached through the soil was made up to
250 cm
3
in a volumetric flask. Ten centimetre cube of this solution
was diluted to 100 cm
3
and the K
1
concentration in the diluted
solution measured by flame photometry. If the K
1
concentration in
this solution is 41 mg cm
À3
, what is the CEC of the soil in cmol
c
kg
À1
?
Concentration of K
þ
in the diluted solution
¼ 41 mg cm
À3
¼ 410 mg cm
À3
in the original 250 cm
3
of solution:
270 Chapter 5
Weight of K in this solution ¼ 410 mg cm
À3
 250 cm
3
¼ 102,500 mg
or 102.5 mg
Atomic weight of K ¼ 39:1
102:5=39:1 ¼ 2:62 mmol K in 10 g soil
or 262 mmol kg
À1
¼ 26:2 cmol kg
À1
As K
1
is monovalent, this is 26.2 cmol of monovalent charge (cmol
c
)
kg
À1
and equal to the CEC of the soil.
Concentrations of exchangeable cations in the above soil were: 3480
mg Ca kg
À1
; 474 mg Mg kg
À1
; 430 mg K kg
À1
; and 161 mg Na kg
À1
.
What is their concentration in cmol
c
kg
À1
, and what is the % base
saturation of the soil?
Atomic weights: Ca, 40; Mg, 24.3; K, 39.1; and Na, 23.
Ca :3480=40 ¼ 87 mmol Ca kg
À1
¼ 8:7 cmol Ca kg
À1
¼ 17:4 cmol
c
kg
À1
Mg :474=24:3 ¼ 19:5 mmol Mg kg
À1
¼ 1:95 cmol Mg kg
À1
¼ 3:9 cmol
c
kg
À1
K :430=39:1 ¼ 11 mmol Kkg
À1
¼ 1:1 cmol Kkg
À1
¼ 1:1 cmol
c
kg
À1
Na :161=23 ¼ 7 mmol Na kg
À1
¼ 0:7 cmol Na kg
À1
¼ 0:7 cmol
c
kg
À1
% base saturation
¼ ½ð17:4 þ 3:9 þ 1:1 þ 0:7Þ=26:2Š  100
¼ 88%:
5.5.3 Ligand Exchange (Chemisorption)
Ligand exchange is the process by which ions are held at a solid phase
surface by covalent bonding. The term chemisorption is often used to
describe this process in order to distinguish it from physisorption, where
coulombic bonds are involved and the process is ion exchange (see
previous section).
271 The Chemistry of the Solid Earth
The important ions held in this way are certain anions, especially
phosphate, and some trace metals; the main surfaces involved are the
iron and aluminium oxides. Unlike ion exchange, the surface charge
plays no part in ligand exchange, which can take place onto positive,
uncharged, or negative surfaces, as these surfaces have a variable charge,
which depends on pH (Figure 7). The ion being chemisorbed replaces a
water molecule or hydroxyl ion (OH
À
) from the surface (Figure 14).
Phosphate, silicate, borate, arsenate, selenite, chromate, and fluoride
are anions for which ligand exchange is important. Nitrate, chloride,
bromide, and perchlorate are not held, while sulfate and selenate may be
weakly held. As a consequence, leaching of nitrate and sulfate from soil
in drainage water can be significant, but very little phosphate is lost in
solution. Of the trace metals, Co, Cu, Ni, and Pb are strongly held on
oxide surfaces by chemisorption, but the process is much less important
for Cd and Zn.
Chemisorption is often described by use of the Langmuir equation:
x/x
m
¼ Kc/(1 þ Kc) (5.41)
where
c ¼ concentration of chemisorbed ion in solution at equilibrium
x ¼ amount of the ion chemisorbed on to the soil
x
m
¼ maximum amount of ion chemisorbed onto the soil
K ¼ a constant related to bonding.
The equation is often used in the linearized form
c/x ¼ c/x
m
þ 1/Kx
m
(5.42)
Fe - OH
2

Fe - OH
2

O
O
Fe - O
Fe - O
O
O
O
P
O
Figure 14 Chemisorption of a phosphate anion on to an iron oxide surface by ligand
exchange
272 Chapter 5
where c can be measured and, knowing the initial concentration and
volume of the solution containing the chemisorbed ion, x can be
calculated. By plotting c/x against c, a straight line will result (if the
Langmuir equation is a suitable model for the process), which will have
a slope of 1/x
m
and an intercept of 1/Kx
m
, allowing the theoretical
maximum chemisorption of the ion to be calculated. In practice,
application of the Langmuir equation is often not strictly valid, as a
straight line relationship is not found. But it is commonly used in order
to obtain a value for x
m
.
5.5.4 Complexation/Chelation
Humic compounds can react with metal cations to form organometallic
complexes:
M
x1
þ OM-LHy "OM-LM
(xÀy)1
þ yH
1
(5.43)
These are particularly stable if more than one bond is formed (chelation)
and are important for heavy metals such as Cu
21
and Pb
21
, and also for
Fe
31
and Al
31
for certain soil-forming processes. Complexation by low
molecular weight organic compounds, such as those in root exudates,
can act as a means of bringing metals into solution, making them more
mobile and bioavailable, but reaction with high molecular weight humic
material is an immobilizing process.
The stability of the metal complex can be expressed as the equilibrium
constant (see also Chapter 4). For example, if Equation (5.43) is
simplified to
M þ L "ML (5.44)
(where M is the metal ion, L the organic ligand, and ML the metal
complex)
K ¼ [ML]/[M][L] (5.45)
While experimentally [M] can be measured and [ML] calculated, it is
difficult to quantify [L], given the polymeric and chemically diverse
nature of soil organic matter.
5.5.5 Precipitation/Dissolution
The concentration of some ions in soil solution is controlled mainly by
the presence of poorly soluble solid phase components. Good examples
of this are iron and aluminium, both of which are highly insoluble at the
pH of most soils, and which are controlled by the solubility of the
273 The Chemistry of the Solid Earth
hydrous oxides. Control of solution concentration by dissolution of an
oxide does not apply to calcium, as the solid phases are too soluble.
When calcium carbonate is present, which is insoluble, it can control the
Ca
21
concentration in soil solution.
Worked example 5.10 – control of ion concentrations in soil solution by
solubility of a solid phase
(a) Amorphous iron oxide is commonly found in soil and its dissolu-
tion to release Fe
31
ions can be represented by the equation
Fe(OH)
3(amorph)
þ 3H
1
"Fe
31
þ 3H
2
O K ¼ 10
3.54
(5.46)
½Fe
3 þ
Š=½H
þ
Š
3
¼ 10
3:54
log Fe
3 þ
¼ 3:54 À 3pH
At pH6; log Fe
3 þ
¼ À14:46;
½Fe
3 þ
Š ¼ 3:5  10
À15
mol L
À1
At pH3; log Fe
3 þ
¼ À5:46;
½Fe
3 þ
Š ¼ 3:5  10
À6
mol L
À1
At pH1; log Fe

¼ 0:54;
½Fe
3 þ
Š ¼ 3:5 mol L
À1
agreeing well with the observed behaviour of Fe
31
, which is soluble
only under very acid conditions. This can be confirmed by using K
sp
¼
10
À36
for Fe(OH)
3
in Worked example 5.5.
(b) Calcium carbonate dissolves to release Ca
21
ions:
CaCO
3
þ 2H
1
"Ca
21
þ CO
2
þ H
2
O K ¼ 10
9.74
(5.47)
Log Ca
21
þ 2pH ¼ 9.74 À log CO
2
For a soil atmosphere with pCO
2
¼10
À2.5
(see Worked example 5.5)
Log Ca
2 þ
¼ 12:24 À 2pH
At pH7; log Ca
2 þ
¼ À1:76;
½Ca
2 þ
Š ¼ 0:02 mol L
À1
At pH5; log Ca
2 þ
¼ 2:24;
½Ca
2 þ
Š ¼ 200 mol L
À1
274 Chapter 5
5.5.6 Soil Processes
A soil receives inputs of ions from the weathering of parent material,
mineralization of organic matter, pollution, and specific additions, such
as fertilizers. The processes described above control the mobility, or
bioavailability, of these ions (Figure 15). Certain ions, such as sodium
and nitrate, are poorly held in soil, and so readily leached out. On the
other hand, phosphate and copper are strongly held. From the point of
view of soil as a source of plant nutrients, it is beneficial for a soil to hold
sufficient nutrients to meet plant requirements, and to hold the nutrients
in a form that can be released to supply the plant over the growing
season. Increasingly, we are using soils as a sink for pollutants, when the
desirable result is that the pollutant is tightly held in order to prevent its
dispersal into the wider environment.
QUESTIONS
(i) Explain the origin and characteristics of the charges on soil
components that make up the CEC of a soil.
(ii) Using the information in Figure 8, how much N, P, and S are
stored per hectare in the soil humus? How much N, P, and S are
released annually per hectare by mineralization of the humus?
It is commonly found that about twice as much P and S is
released from the soil than predicted, but that the amount of N
agrees well with the prediction. What process could account for
this?
A soil solution contains 3 Â 10
À6
mol PO
4
-P L
À1
, 5 Â 10
À4
mol SO
4
-S L
À1
, and 2 Â 10
À3
mol NO
3
-N L
À1
. If the annual
drainage is 250 mm of water, how much P, S, and N are lost
annually per hectare by leaching? (P ¼ 31; S ¼ 32; and N ¼ 14).
(iii) A typical rate of addition of Pb in sewage sludge to agricultural
soils in the UK is 1200 g Pb ha
À1
year
À1
. If this amount is added
to a soil of bulk density 1.2 g cm
À3
containing 5% humus with a
binding capacity of 80 cmol
c
kg
À1
, what percentage of the
binding capacity to a depth of 20 cm is used annually to hold
the lead? (Assume that all the added Pb is bound to the humus.
Pb ¼ 207.)
(iv) Using the values for solubility product below, and assuming
that the solubility of the hydroxides controls the metal ion
concentration in solution, calculate the theoretical concentra-
tions of Fe
21
, Fe
31
, and Cr
31
at pH 2, 5, and 7.
275 The Chemistry of the Solid Earth
Soil
Natural
inputs:
Atmospheric
deposition
Deposition from
water
Cycling through
vegetation
Anthropogenic
inputs:
Atmospheric
contamination
Water
contamination
Wastes added to
soil
Fertilizers
Losses:
Volatilization to
atmosphere
Offtake in
crops
Losses:
Leaching in
drainage water
Erosion of soil
Soil
solution
Ion exchange -
physisorption
Ligand exchange -
chemisorption
Chelation
Precipitation
Figure 15 An overview of soil processes
276 Chapter 5
K
sp
Fe(OH)
2
¼ 10
À14
; Fe(OH)
3
¼ 10
À36
; Cr(OH)
3
¼ 10
À33
What does this tell you about the solubility of these ions?
Does this agree with their observed behaviour in soil?
(v) A soil with a bulk density of 1.2 g cm
À3
contains 1% FeS
2
. How
much CaCO
3
is required per hectare to neutralize the acid
produced to a depth of 20 cm? (Assume that the FeS
2
oxidizes
completely. Fe ¼ 56; S ¼ 32; Ca ¼ 40; C ¼ 12; and O ¼ 16.).
(Hint: look at Worked example 5.1 and combine Equations
(5.16) and (5.17) to get an overall reaction for the oxidation of
pyrite.)
(vi) Iron oxides in soil undergo reduction to produce Fe
21
ions-
Fe(OH)
3
þ 3H
1
þ e
À
"Fe
21
þ 3H
2
O E
0
¼ 1.057 V
What is the concentration of Fe
21
ions in solution in a soil of
pH 7 at 100 and 0 mV?
(vii) 1.00 g samples of a soil were shaken with 50 cm
3
of different
solutions of known zinc concentration. After 1 h, the soil
suspensions were filtered and the concentration of zinc in the
filtrate measured, with the following results:
Initial concentration
(mg Zn L
À1
)
Final concentration
(mg Zn L
À1
)
7.5 1
10 2
20 5
30 10
45 21
60 34
In each case, calculate the weight of zinc held by 1 g of soil. Plot
the graph of weight of Zn held per gram (y-axis) against the final
concentration of Zn.
Fit the data to the Langmuir equation and plot the graph.
Obtain values for x
m
and K.
(viii) The equilibrium between Fe
31
ions in soil solution and iron
oxides in soil has been described by the equation
Fe(OH)
3 soil
þ 3H
1
"Fe
31
þ 3H
2
O log K ¼ 2.70
277 The Chemistry of the Solid Earth
(Note, this is a different form of iron oxide to that used in
Worked example 5.10, hence a different value for K).
Derive the relationship between the concentration of Fe
31
ions in solution and pH.
Use this equation to plot the concentration of Fe
31
over the
pH range 1–9.
How well does this information agree with the Fe
31
concen-
trations calculated in Question 4?
(ix) What properties of a soil would you investigate in order to learn
about its ability to hold and supply P and K to crops?
(x) What properties of soil would you investigate in order to learn
about the ability of a soil to act as a sink for pollutants?
REFERENCES
1. S.A. Barber, Soil Nutrient Availability, Wiley, New York, 1995.
2. J.B. Dixon and D.G. Schulze (eds), Soil Mineralogy with Environ-
mental Applications, Soil Science Society of America, Madison, WI,
2002.
3. D.J. Greenland and M.H.B. Hayes (eds), The Chemistry of Soil
Constituents, Wiley, Chichester, 1978.
4. D.J. Greenland and M.H.B. Hayes (eds), The Chemistry of Soil
Processes, Wiley, Chichester, 1981.
5. W.L. Lindsay, Chemical Equilibria in Soils, Wiley, New York, 1979.
6. M.B. McBride, Environmental Chemistry of Soils, Oxford University
Press, New York, 1994.
7. R.G. McLaren and K.C. Cameron, Soil Science, 2nd edn, Oxford
University Press, Auckland, 1997.
8. J.J. Mortvedt, F.R. Cox, L.M. Shuman and R.M. Welch, Micro-
nutrients in Agriculture, 2nd edn, Soil Science Society of America,
Madison, WI, 1991.
9. D.L. Rowell, Soil Science: Methods and Applications, Longman
Scientific & Technical, Harlow, 1994.
10. G. Sposito, The Chemistry of Soils, Oxford University Press, New
York, 1989.
11. F.J. Stevenson, Humus Chemistry, Wiley, New York, 1982.
12. R.E. White, Principles and Practice of Soil Science, 3rd edn, Black-
well Science Ltd., Oxford, 1997.
13. A. Wild (ed), Russell’s Soil Conditions and Plant Growth, 11th edn,
Longman Scientific & Technical, Harlow, 1988.
278 Chapter 5
CHAPTER 6
Environmental Organic Chemistry
CRISPIN J. HALSALL
Environmental Science Department, Lancaster University, Lancaster LA1
4YQ, UK
6.1 INTRODUCTION
Environmental Organic Chemistry (EOC) is an exciting branch of chem-
istry that has developed over the last few decades, and is probably best
known for the study into the fate and behaviour of anthropogenic (man-
made) pollutants. EOC, however, cannot be restricted to organic pollut-
ants and their behaviour, but also encompasses the myriad of organic
molecules produced by nature and their associated biogeochemistry. This
area of chemistry is coupled to the recent advances in analytical tech-
niques, particularly improvements in chromatography and the rise in
‘hyphenated’ techniques, such as GC-MS and LC-MS. The sensitivity of
contemporary bench-top instruments allows detection of analytes in
environmental samples, down to as low as a few picogrammes (pg)
(10
À12
g) on the chromatography column. Recently, the improvements
in LC-MS technology, has resulted in affordable, yet sensitive instrumen-
tation that allows separation and detection of a mixture of polar, water-
soluble analytes. The use of LC avoids derivatisation steps of highly polar
analytes required as a pre-requisite to GC analysis. The different sources
now available to LC-MS, including atmospheric pressure photoionisation
and chemical ionisation, allows a high degree of selectivity for a wide
number of analytes of varying molecular weights, polarity and aqueous
solubility. This enables analysis of pollutant degradates and metabolites
in aqueous systems and has led to the screening of pharmaceuticals,
veterinary drugs and antibiotics in both surface and ground water.
1–3
The traditional organic chemist often works in a highly controlled
environment, where variables may be reduced to several reactants under
carefully controlled temperatures and pressures; the goal to produce a
279
product of the highest possible yield. The EOC, on the other hand, has
to understand the chemistry and reactions of an organic molecule but
under earth’s near-surface conditions, with varying temperature (À50 1C
to þ50 1C) and atmospheric pressures (950 to 41000 hectoPa (hPa)). In
addition, the laboratory analyst in a chemical company, has the job of
qualifying the purity of products to some standard specified by the
customer. The environmental chemist however, has the difficult task of
extracting, purifying and quantifying the same chemicals, their un-
wanted by-products (and possibly their degradates) from environmental
media (e.g. soil, water, biota, etc.) to a high degree of precision and
accuracy. Measuring specific chemicals in different environmental media
and understanding how the chemistry in these media ‘fits together’
presents a considerable challenge, and often results in the environmental
chemist returning to the laboratory to simulate a particular process.
This chapter will explore aspects of EOC in relation to the environ-
mental behaviour and fate of anthropogenic pollutants and will explore
the physical and chemical processes that result in their environmental
partitioning and degradation; specifically photodegradation for the
latter. In each case practical examples and measurement techniques will
be presented and illustrated.
6.2 THE DIVERSITY OF ORGANIC COMPOUNDS
The wide array of organic compounds subject to research within EOC,
encompass a broad range of physical–chemical properties, but can be
categorised according to either molecular weight, volatility and/or
reactivity. Figure 1 provides examples of a range of molecules that have
vapour pressures spanning orders of magnitude, and are subject to
research because of their interesting chemistry either in the atmosphere,
aquatic systems and/or soil and sediments.
Many of the more volatile compounds (C
1
ÀC
6
) emitted into the atmos-
phere have an important impact on atmospheric photochemical processes.
Oxidation of short-chain alkanes largely through reaction with the OH
radical, form short-lived peroxy (HO
2
.
) and alkoxy radicals (RO
2
.) that are
important for converting NO to NO
2
in the polluted atmosphere and hence
allowing the build up of ground-level ozone (O
3
) during warm sunny
weather (see Chapter 2). For higher molecular weight compounds ( ZC
5
)
the isomerisation of alkoxy radical intermediates gives rise to hydroxyl
carbonyl products containing ÀOH, ÀCOOH and ÀC
Q
O groups. These
products comprise the major fractions of organic aerosol, and a growing
body of research literature is dedicated to understanding the oxidation
products and reaction mechanisms of vapour hydrocarbons to less volatile,
280 Chapter 6
more polar condensates involved in aerosol formation and growth.
4
Monoterpenes (C
10
) released from different types of vegetation, contain
unsaturated double bonds and are therefore susceptible to reaction with O
3
.
The reaction of a-pinene, for example, gives rise to a number of carbonyl
and mono- and dicarboxylic acids, including pinonaldehyde and pinic acid
which have been detected in forest aerosols.
5
Semi-volatile organic compounds arise from a multitude of sources,
both anthropogenic and natural, but include the persistent organic pol-
lutants, many of which are halogenated aromatic compounds found at
trace levels in the environment, but are dispersed widely across the globe.
For aliphatic compounds such as petroleum hydrocarbons, the semi-
volatile constituents include longer chain alkanes (4C
15
), both normal
(n-alkanes), branched (iso-alkanes) and cyclic alkanes (cyclo-alkanes or
naphthenes) as well as a range of polycyclic compounds or terpanes
including tricyclic carpanes, tetracyclic hopanes and pentacyclic steranes.
Many of the hopanes and steranes are largely involatile, and in the
atmosphere are predominantly associated with particles.
6
They are im-
portant constituents of crude oils, arising principally from the decay of
bacterial/biotic matter and serve as useful biomarkers for different fuel
types, and are also widespread in sediments and soils from both biogenic
Cl
OH
Cl
Cl
10
7
10
6
10
5
10
4
10
3
10
2
10
1
10
0
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
O
O
O
Cl
Cl
Cl
Cl
Cl
H
H
H
H
H
H
Cl
Cl
Cl
pinonaldehyde
(from α-pinene)
n-decane
α-pinene
(monoterpene)
toluene
CH
3
benzene n-hexane
dichloromethane
CH
2
Cl
2
isoprene
propane
ethene
methane
acetone
CH
4
Cl
Cl
Cl
Cl
Cl
P/Pa (at 298K)
2,4- dichlorophenol
γ-HCH
(organochlorine insecticide)
1,3- dimethylnaphthalene
(alkylated-PAH)
fluoranthene (PAH)
n-heptadecane (n-C
17
)
trichlorinated naphthalene
(PCN)
pentachlorinated biphenyl
(PCB)
benzo[a]pyrene (PAH)
Figure 1 Approximate vapour pressures (P) (10
7
À10
À6
Pa) for a diverse range of
organic compounds, many of which are mentioned in this chapter. Note the use
of common/trivial chemical names rather than IUPAC nomenclature
281 Environmental Organic Chemistry
and petrogenic sources. The semi-volatile polycyclic aromatic hydrocar-
bons (PAHs) and their alkylated derivatives are generally less abundant
than the alkanes and terpanes of similar carbon number, but are present
in oil and liquid fuels and are also produced during combustion processes
(pyrolysis), and are present in soil and sediments from both petrogenic
and pyrolytic sources. The five-ringed benzo[a]pyrene is a notable exam-
ple, and is classed as a probable human carcinogen, present in urban
environments chiefly from the combustion of fossil fuels.
The involatile, complex polymeric organic matter present in soils and
sediments is commonly referred to as ‘humic substances’, and probably
forms through a series of oxidation and condensation reactions between
polyphenols, polysaccharides and polyamino acids of plant and microbial
origin.
7
There is no commonly accepted structure of humic substances, with
molecular weights and molecular formulae open to debate, and varying
widely between different soil and sediment types. Extraction of soils with
water and/or organic solvents generally yield only a small fraction of soil-
carbon present as humic substances, but the accepted practice of extracting
soils with aqueous alkali (0.5% NaOH), followed by centrifugation of the
soil/sediment suspension with subsequent acidification of the supernatant,
yields the acid-insoluble humic fraction known as humic acid. Any organic
material left in solution is referred to as fulvic acid and the remaining
insoluble material is referred to as humin.
8
These operationally defined
fractions prove very useful for conducting sorption and fate experiments
for organic pollutants present in soil/sediment systems, where humic sub-
stances play an important role in the soil chemistry of organic compounds.
Humic and fulvic acids give rise to dissolved organic material in water, and
are complex organic macromolecules with a wide variety of functional
groups, primarily carboxylic and phenolic groups, and to a lesser extent
amino (e.g. -NH
2
) and thiol (-SH) groups. These macromolecules have a
wide range of molecular weights (Eo500 to 410,000 g mol
À1
) and
various humic acid fractions have been separated by gel-permeation chro-
matography (or size-exclusion chromatography) with their structural and
chemical characteristics investigated using
1
H- and
13
C-NMR, and pyr-
olysis-GC-MS.
9
The large surface areas of these molecules provide ideal
surfaces for sorption by other organic molecules, including semi-volatile
organic contaminants such as PAHs and pesticides, providing active sites
for surface-based, heterogeneous chemical reactions.
6.2.1 Identifying Sources of Hydrocarbons
Distinguishing between different sources of hydrocarbons including al-
kanes and PAHs for example, is of fundamental importance for source
282 Chapter 6
apportionment of pollution, as well as in petroleum geochemistry to
indicate the origin and thermodynamic maturity of organic matter in
sediments. A commonly used index to broadly distinguish between ant-
hropogenic and biogenic sources of hydrocarbons, present in any envi-
ronmental compartment, is the Carbon Preference Index (CPI). CPI is
usually applied to the homologous series of semi-volatile n-alkanes with
carbon chain lengths ranging from BC
15
to C
35
, where the CPI is simply
the concentration ratio of the summed ‘odd-numbered’ chain lengths over
the ‘even-numbered’ chain lengths over a specified chain-length range.
The premise here is that recent biogenically derived n-alkanes (e.g. plant
waxes, biota exudates) tend to favour odd-carbon numbered chain
lengths (typically within the range C
25
to C
35
) whereas aged organic
material, such as petrogenic hydrocarbons that have undergone ageing
over geological timescales generally do not exhibit this odd-carbon
number preference. Therefore, environmental samples with a CPI 41,
suggest that the aliphatic hydrocarbons, have arisen through biogenic
input, whereas a CPI of o1, suggests petrogenic (e.g. fossil fuel) sources.
As an example, suspended particle matter (SPM) filtered from seawater
samples collected in the Black Sea, showed high CPI values of 3.81–13.1
in offshore locations, where the SPM was considered to be of algal origin
(where CPI
marine
¼ SC
15À25
/SC
14À24
).
10
Much lower CPI values were
observed closer to the Danube estuary, and were indicative of petrogenic
derived hydrocarbons, presumably due to river discharges of petroleum
products. There are other useful aliphatic indices or markers that are used
in conjunction with the CPI to provide evidence of oil ‘weathering’ or to
apportion carbon sources as either petrogenic or of recent biogenic origin.
The ubiquitous and rather persistent branched alkanes, pristane (C
19
) and
phytane (C
20
), are often ratioed to n-heptadecane (C
17
) and n-octadecane
(C
18
) respectively, as supporting evidence of either biogenically derived or
petrogenic hydrocarbons to sediments and aqueous systems (both pristine
and phytane closely elute with these two n-alkanes on a low-polarity GC-
column). For instance, a high n-C
17
/pristane ratio (410), would indicate
biogenically derived hydrocarbons, whereas a low ratio (o3) would
indicate a carbon source depleted in n-C
17
, perhaps indicative of pet-
rogenic carbon sources.
PAHs and their alkylated derivatives are also used to distinguish
between pyrolytic and petrogenic inputs to sediments and soils and
are often used in conjunction with aliphatic indices to discriminate
hydrocarbon sources. The lower molecular weight 2- to 4-ringed PAHs
and their alkylated versions comprise a small, but significant, component
of crude oils and liquid fuels. Ratios of parent PAHs (non-alkylated) as
well as parent to alkylated versions are frequently used to distinguish
283 Environmental Organic Chemistry
petrogenic sources vs. pyrolytic sources (both natural and anthropogenic)
for aromatic hydrocarbons in soil/sediment systems.
11
6.3 THE FATE OF ORGANIC CONTAMINANTS
There are thousands of organic chemicals entered into the international
databases as part of legislative programmes aimed at assessing the risk
they pose to human health and the environment. For example, in the
European Union, the European Inventory for Existing Chemical Sub-
stances and the European List of Notified Chemical Substances include
over 100,000 commercial substances.
12
Similarly in the US, the Office for
Pollution Prevention and Toxics (OPPT) as part of the US-Environmental
Protection Agency (EPA) maintains lists of high-production volume
chemicals as well as persistent bioaccumlative toxins (PBTs). The increas-
ing demand for risk assessment to examine substances with respect to their
environmental persistence, ability to bioaccumulate and potential for
toxicity, increases the demand for reliable physical–chemical property
data, upon which to conduct environmental fate and degradation studies.
In this respect, a risk assessment is conducted to ascertain the likelihood or
probability of some harm arising to either humans or the environment due
to exposure to that chemical substance. In order to assess exposure and
understand chemical fate, then intimate knowledge of both the chemical
use (quantity released) and behaviour (environmental transport, partition-
ing and transformation/degradation) are required. As Schwarzenbach
et al.
13
have so elegantly described in their comprehensive text on EOC;
organic chemicals once present in the environment are subject to essen-
tially two types of process. The first involves their environmental transport
within, and transfer between, environmental phases and the second in-
volves their chemical alteration (transformation/degradation) driven by
chemical and/or biological processes. In reality, within any given environ-
mental system, these processes may occur simultaneously and different
processes may strongly influence one another.
6.4 CHEMICAL PARTITIONING
The transfer of chemicals between two or more environmental com-
partments or phases can be described by equilibrium partitioning, and
knowledge of this partitioning is essential for understanding and de-
scribing chemical fate in the environment. Chemical partitioning takes
place between adjacent phases such as between a solid and a liquid
(dissolution), a liquid and a gas (volatilisation), a solution and a solid
surface (adsorption) or a solution and an immiscible liquid (solvent
284 Chapter 6
partitioning). The net transport of an organic compound from one
phase to another (e.g. air to water) is limited by equilibrium constraints
and can be quantified according to a partitioning constant or coefficient
(K). This is simply defined as the ratio of the concentration (C) of the
chemical present in each phase (e.g. 1 and 2) at equilibrium; the point at
which the chemical potential in each phase is equal and there is no
longer net transfer in one direction. K can be represented as
K
1;2
¼
C
1
C
2
ð6:1Þ
In strict terms, K is expressed as the ratio of the mole fractions (x) of a
chemical within each phase (for example, this could be the mole fraction
of a chemical present in a gaseous or liquid mixture). However, in
environmental chemistry, the common way of expressing chemical
concentration is not by mole fractions but as a molar concentration
(mol L
À1
or molarity, M), although it is worth pointing out that the
volume (L or dm
3
) may vary according to changes in temperature and
pressure and should be normalised to standard temperature (298 K) and
pressure (101,325 Pa (or 1 atm)). Furthermore, when dealing with one
phase that is solid, it is often more appropriate to deal with concentra-
tions as amount per mass to avoid having to estimate phase densities. A
mole fraction can be converted to molar concentration (M) according to
M ¼
xðmol=molÞ
VðL=molÞ
ð6:2Þ
where V is the molar volume of the mixture or solution. For aqueous
solutions relevant for environmental scenarios, it is possible to ignore
the contribution of the organic chemical to the molar volume of the
mixture due to the typically low concentrations of a chemical pollutant
present in a body of water. In this case, V is simply set as the molar
volume of water (V
w
¼ 0.018 L mol
À1
at 25
o
C).
13
The term partitioning constant or coefficient refers to one chemical
species in each phase (for example, ionisable chemicals present in water
may exist in both neutral and dissociated forms and therefore each
would have a separate partitioning coefficient). For well-defined phases,
such as pure water or the pure liquid state of the chemical, then
partitioning with another equally well-defined phase such as air results
in the use of the term partitioning constant. The Henry’s Law constant
describing chemical partitioning between pure air and water is one
example. Distribution ratios on the other hand, such as the soil-water
285 Environmental Organic Chemistry
distribution ratio (K
d
), describe partitioning between a heterogeneous
solid phase (soil) and soil-water (containing a variety of dissolved solids
and organic material). Furthermore, a distribution ratio accounts for all
the speciated forms of a particular chemical, as well as the various
different sorption mechanisms and correctly describes the distribution of
a chemical rather than a particular partitioning process. An example of a
useful partitioning coefficient applied to soils and sediments is the
organic-carbon to water partitioning coefficient (K
oc
), which specifically
describes chemical partitioning between the organic-carbon fraction of a
soil or sediment and water and is frequently used to describe pesticide
fate in agricultural soils.
6.4.1 Important Partitioning Coefficients
There are several important partitioning coefficients, besides the funda-
mental properties of vapour pressure and aqueous solubility, which are
essential for understanding chemical transfer in the environment and
these are illustrated in Figure 2 and include the air/water (K
aw
), n-octanol/
water (K
ow
) and n-octanol/air (K
oa
) partitioning coefficients. Indeed,
chemical vapour pressure (the ‘solubility’ of a chemical in air) and
aqueous solubility explain the ‘partitioning’ of a chemical from the
pure-liquid or solid-state into air and water, respectively. Transfer of
either vapour or dissolved chemical to other environmental compart-
ments, media or phases can be explained by specific partition coefficients.
ORGANIC PHASE
‘Octanol like’
WATER AIR
Kow Koa
Kaw
Chemical
P S
e.g. fats/lipids/waxes
organic carbon in soil
Figure 2 Key physical–chemical properties that control the environmental partitioning of
an organic chemical. The fundamental properties of vapour pressure (P) and
aqueous solubility (S) determine the partitioning from the pure liquid or pure
solid-state of the chemical into air and water, respectively
286 Chapter 6
6.4.1.1 Octanol-Water Partitioning Coefficient (K
ow
). Octanol serves
as a very useful surrogate of fats, lipids and organic phases present in the
environment. This is largely attributable to octanol having a similar
carbon to oxygen ratio (8:1) as fatty acids and lipids. As a result K
ow
is
used to represent chemical partitioning between lipids and water (where
lipids and fats can be viewed as ‘octanol-like solvents’) and is an
important chemical property used in the fields of biology and pharmacy,
where K
ow
is represented by the term ‘P’ for partitioning coefficient. In
essence, K
ow
is the ratio of the equilibrium concentration of a chemical
between octanol (mol m
À3
) and water (mol m
À3
) and is a measure of a
chemical’s ‘water hating’ tendency or hydrophobicity. As Mackay
14
points out, most organic chemicals have a fairly constant solubility in
octanol (200–2000 mol m
À3
) but very different solubility in water and it
may be misleading to describe K
ow
as a chemical’s ‘love of fats’ or
lipophilicity. As the range of K
ow
for environmental contaminants is
large (over orders of magnitude), log K
ow
values are often reported.
Perhaps the most common application of K
ow
is for predicting the
bioconcentration of low-polarity hydrophobic contaminants from water
into aquatic biota. A bioconcentration factor (BCF) can be represented
as
BCF ¼
C
org
C
w
ð6:3Þ
where C
org
is the actual concentration determined in an organism (e.g.
fish), or some ‘compartment’ of the organism (e.g. lipids), and C
w
is the
truly dissolved concentration of the chemical in water. From empirical
studies that have examined a range of different organisms and chemi-
cals, BCF may be predicted from simple linear relationships with K
ow
.
For example, Mackay
15
described the BCF in fish, by examining hun-
dreds of organic chemicals, as
BCF ¼ 0:048 K
ow
ð6:4Þ
The constant 0.048 representing the E5% lipid content of fish, or as
Mackay describes, about 5% octanol by volume. However, relationships
between BCF and K
ow
appear to break down for chemicals with log
K
ow
47, as these ‘superhydrophobic’ substances may have difficulty
crossing cellular membranes (i.e. they have a low bioavailability) or
are rapidly egested from the organism. There is, in fact, little consensus
on the reasons for the breakdown in the linear relationship between
BCF and chemicals with log K
ow
47, but both Borga˚ et al.
16
and
Boethling et al.
17
point out that the experimental artefacts associated
287 Environmental Organic Chemistry
with measuring the freely dissolved chemical are likely to provide large
uncertainties in the BCFs. Furthermore, bioconcentration is unlikely to
be a significant exposure pathway for these ‘superhydrophobic’ chem-
icals relative to dietary intake.
K
ow
is also used to describe partitioning to general organic phases
within the environment and K
oc
(introduced above) can be directly
estimated from K
ow
according to the empirically derived relationship
derived initially by Karickhoff
18
and refined by Seth et al.
19
where
K
oc
¼ 0:35 K
ow
ð6:5Þ
this relationship is useful for calculating the sorption of chemicals to
soils and sediments from water; specifically to the organic carbon
fraction. It is worth noting that K
oc
represents a solid/liquid partition
coefficient and as such has units of L kg
À1
, whereby K
oc
can be
represented as
K
oc
¼
C
oc
ðmoles=kgÞ
C
w
ðmoles=LÞ
ð6:6Þ
where C
oc
is the chemical concentration sorbed to the natural organic
carbon fraction in soil (B0.02 or 2%) and C
w
is the dissolved water
concentration. As K
ow
is dimensionless, the constant in Equation 6.5 has
units of L kg
À1
. Experimentally, K
oc
is determined by introducing (or
‘spiking’) a chemical into a water/soil mixture (slurry) that is stirred at a
constant temperature, followed by filtration and analysis of the water at
different time intervals. The resulting K
d
value is then divided by the
organic carbon fraction (f
oc
) of the test soil, whereby
K
oc
¼
K
d
f
oc
ð6:7Þ
Multiplying K
d
(which also has units of L kg
À1
) by soil density (B2.4 kg
L
À1
) allows the dimensionless form of K
oc
to be used.
6.4.1.2 Henry’s Law Constant and Air-Water Partitioning (K
aw
). Air-
water partitioning is described by the Henry’s Law constant (H), which
is defined as the ratio of the partial pressure (p) of a chemical in the air to
its mole fraction (or molar concentration) dissolved in water (C
w
) at
equilibrium, according to
H ¼
pðPaÞ
C
w
ðmol=m
3
Þ
ð6:8Þ
288 Chapter 6
H therefore has the units of Pa m
À3
mol
À1
and can be estimated by
ratioing a chemical’s liquid-phase saturation vapour pressure (usually
the sub-cooled liquid vapour pressure) over its aqueous solubility, at
some reference temperature. Note that the vapour pressure (P) can be
readily converted into ‘solubility’ with units of molar concentration by
applying the ideal gas law
PV ¼ nRT ð6:9Þ
Rearranging this equation to n/V (mol m
À3
) ¼ P/RT, where RT is the
gas constant – temperature product (8.314 Pa m
3
mol
À1
K Â K), allows
the following expression
P
RT Á C
w
¼
C
a
C
w
¼ H
0
or K
aw
ð6:10Þ
where P/RT is the air concentration (C
a
) with the same units as C
w
, and
H
0
is the ‘dimensionless’ H or K
aw
and can also be obtained by simply
dividing H by RT (note that the units cancel), where T is the relevant
environmental temperature in K.
Like K
ow
, values of H vary tremendously for the range of organic
compounds of interest in the environment. For example, short-chain
alkanes with their high vapour pressures and low aqueous solubilities
have values of H that are orders of magnitude higher than alcohols,
which are highly soluble in water and have lower vapour pressures. For
certain pesticides and other semi-volatile organic compounds, which
may persist in the environment, their lower vapour pressures generally
result in relatively low values of H, but often their very low solubility can
result in higher than expected values of H. As a consequence, these
chemicals (particularly sparingly soluble organochlorine pesticides) ap-
preciably partition to air from bodies of water in which they may be
residing (i.e. run-off from agricultural regions). In addition, they will not
be efficiently removed from the atmosphere by rainfall and as a result
may be transported long-distances by the prevailing wind. Table 1
provides examples of select chemicals and their calculated H values
using both saturated vapour pressure and aqueous solubility data.
Clearly, n-hexane has the highest value of H out of this group of
chemicals, but interestingly H for benzene is 557, B200-fold greater
than DDT and B4000-fold greater than chlorpyrifos, yet both pesticides
are relatively involatile, with vapour pressures some 600 million and 85
million times less than benzene, respectively. The low solubility of these
pesticides ensure that H is higher than may be expected and both
pesticides partition appreciably out of water.
289 Environmental Organic Chemistry
Temperature is a key parameter for controlling H or K
aw
, thereby
strongly influencing air-water partitioning of chemicals in the environment.
A good deal of effort is expended in deducing temperature-dependent H for
contaminants of concern, which is not an easy task for low-polarity
hydrophobic organic chemicals (HOCs) with poor solubility.
Figure 3 shows a schematic diagram of the typical apparatus used to
measure H for these types of chemical. In essence the major component is
the reactor vessel, which contains a large volume of deionised water
(B0.5–10 L) spiked with a known concentration of the HOC in question.
The chemical is introduced by first dissolving the chemical in an organic
solvent which is miscible with water (e.g. acetone), and an aliquot added
to the water in the reactor vessel. Care must be taken that the concen-
tration does not exceed the aqueous solubility of the chemical and usually
the concentration in the vessel is only a few percent of the aqueous
solubility, resulting in a very low concentration, B1–2 mg L
À1
. Clean,
water-saturated air (or N
2
) is then bubbled or sparged through the reactor
vessel and the exiting air passed through a vapour-trap to collect the
chemical present in the air stream. The chemical quantity on the vapour
trap can be turned into a time-averaged air concentration (C
a
), by
calculating the volume of air that has passed through the trap. H is
calculated by ratioing C
a
to the average water concentration in the reactor
vessel (C
w
) (see Equation 6.10) determined from analysis of water samples
taken at the start and end of the experiment. Each gas-stripping run will
be replicated to assess the precision, and new experiments conducted at
different temperatures to provide the regression parameters to derive
temperature-dependent values of H. Artefacts are always present, not
least keeping the reactor vessel at a uniform temperature, but also
preventing water from condensing in the vapour trap (particularly at
Table 1 Select physical–chemical property data for four relatively volatile
chemicals and two semi-volatile insecticides: p,p
0
-DDT and chlorpyr-
ifos (a currently used pesticide). Note that the chemicals are arranged
in order of volatility (Data sourced from Mackay
14
)
Chemical
Molecular mass
(g mol
À1
)
Vapour
pressure (P)
(Pa)
Aq. solubility
(S) (mol m
À3
)
Henry’s Law
constant (H)
(Pa m
À3
mol
À1
)
Chloroform 119.4 23,080 68.7 336
n-hexane 86.2 20,200 0.11 18,364
Benzene 78.1 12,700 22.8 557
Phenol 94.1 70.6 871 0.081
Chlorpyrifos 350.6 0.00015 0.0011 0.14
p,p
0
-DDT 354.5 0.00002 0.0000087 2.3
290 Chapter 6
higher temperatures), and accounting for the loss of water through
evaporation. Furthermore, the change in water volume in the reactor
vessel when extracting aliquots for chemical analysis should also be taken
into account
21
and efforts directed at shielding the apparatus from
laboratory light when determining H for light-sensitive chemicals.
6.4.1.3 Octanol-Air Partitioning Coefficient (K
oa
). Partitioning of a
chemical between some organic phase and air is often described using
K
oa
. Examples of terrestrial organic phases include organic carbon in soil,
the waxy cuticle and lipid portion of vegetation and the organic film that
coats atmospheric particle matter and partitioning between these phases
and air for a number of chemical groups have been successfully described
using K
oa
.
22–24
Laboratory-based measurements of temperature-dependent
K
oa
values have been derived for a number of semi-volatile chemical
groups, including PCBs
25,26
PAHs,
27
polychlorinated naphthalenes
(PCNs)
27
and organochlorine pesticides.
28
K
oa
can be described as the
ratio of the chemical (solute) concentration in octanol to the concentration
in air at equilibrium, represented as
K
oa
¼
C
o
C
a
ð6:11Þ
Figure 3 Schematic diagram of the gas-stripping apparatus used to measure temperature-
dependent Henry’s Law constants (H) for semi-volatile organic compounds
(SVOCs)
From Bamford et al.
20
courtesy of SETAC press
291 Environmental Organic Chemistry
where C
o
and C
a
represent the equilibrium concentrations in octanol
and air respectively (mol m
À3
) and hence K
oa
is dimensionless. K
oa
may
be estimated as the ratio of K
ow
over K
aw
i.e. K
oa
¼K
ow
/K
aw
. As K
aw
¼H/
RT then K
oa
can be expressed as
K
oa
¼
K
ow
RT
H
ð6:12Þ
As there are very few direct measurements of K
oa
, application of Equation
6.12 is useful, although this approach may have limited utility, as reliable
values of H and K
ow
for a particular chemical may be scare. Furthermore,
the validity of Equation 6.12 is brought into question when comparing
calculated K
oa
values with actual measurements
26
and extensive addi-
tional measurements of K
oa
are required for a wide number of chemicals
that occur in the environment. As with K
ow
and K
aw
, values of K
oa
may
vary over orders of magnitude within any particular chemical class, and
therefore K
oa
is often reported as a log value.
6.4.2 Temperature Dependence
Before proceeding, it is worth turning briefly to thermodynamics to
provide some fundamental aspects to partitioning coefficients and,
importantly, their relationship to temperature. Wide variations in tem-
perature experienced in the environment can greatly alter the partition-
ing behaviour of a chemical, and this will be demonstrated later when
comparing chemical behaviour between different latitudes with notable
temperature differences.
As with any chemical reaction, movement of a chemical from one phase
to another (i.e. liquid to gas) results in a change in the energy status of the
system. A partitioning coefficient is related to the (Gibbs) free energy of
transfer of the chemical between the two phases (DG, J mol
À1
). Where DG
relates both the enthalpic and entropic effects that result from the changes
occurring in either phase (i.e. intermolecular interactions), through both
the removal and addition of molecules of the chemical. The relationship
between DG and the change in enthalpy (or heat energy) of transfer (DH, J
mol
À1
) and entropy (DS, J mol
À1
K
À1
) is given by the Gibbs–Helmholz
equation: DG ¼ DH–TDS. Knowledge of the change in enthalpy for a
certain partitioning process is particularly useful and is sought by envi-
ronmental chemists to allow derivation of temperature-dependent parti-
tioning. The relationship between K and DG is given by
K ¼ constant:e
ÀDG=RT
or ln K ¼ À
DG
RT
þ lnðconstantÞ ð6:13Þ
292 Chapter 6
K is therefore a function of temperature through the term RT, where R is
the gas constant, 8.314 J mol
À1
K and T is the temperature expressed in
Kelvin (K). The value of the constant given in Equation 6.13 depends on
how the abundance of the solute or chemical is expressed i.e. partial
pressure, mole fraction or molar concentration. For mole fraction the
constant has a value of 1, whereby ln 1 ¼ 0 and can therefore be ignored.
Rearranging Equation 6.13 to solve for DG, and then combining with
the Gibbs–Helmholz equation results in
ÀRT ln K ¼ DH À TDS ð6:14Þ
Hence; ln K ¼ À
DH
RT
þ
DS
R
ð6:15Þ
It therefore follows that an experimentally determined plot of ln K
against 1/T (1/K) will yield a slope of ÀDH/R, and an intercept of DS/R
(DH and DS are considered to be constant over a small temperature
range). In laboratories measuring partition coefficients for environmen-
tal fate, then À10 to 45 1C is a typical temperature range. Equation 6.15
is usually expressed in the form:
ln K ¼ À
m
T
þ b ð6:16Þ
where m is the slope of the line and hence Rm ¼ DH. Once DH is
established then K can be adjusted to any environmentally relevant
temperature according to the integrated form of the van’t Hoff equation
ln KðT
2
Þ ¼ ln KðT
1
Þ À
DH
R
1
T
2
À
1
T
1

ð6:17Þ
where T
1
is the reference temperature (298 K) at which K(T
1
) and DH have
been measured and T
2
is the temperature of interest. For many organic
chemicals that persist in the environment, careful laboratory measurements
of a particular partitioning coefficient over a range of temperatures may
not exist, therefore DH
0
(the enthalpy for the partitioning process at stand-
ard state, 101 kPa and 298 K) is often used in Equation 6.17.
Case study and worked example – Calculating water concentrations of
Lindane
To illustrate the effect that temperature has on a partition coefficient
and use some of the equations above, it is worth examining the
293 Environmental Organic Chemistry
air-water partitioning of a pesticide. Lindane is an organochlorine
insecticide that comprises of almost 100% g-hexachlorocyclohexane
(g-HCH). The chemical has been recently nominated as candidate
POP chemical and it is widely distributed in the global environment.
Indeed this chemical is routinely monitored in arctic air
29,30
and is
present in the polar environment largely through long-range atmos-
pheric transport. Let’s assume that g-HCH has an air concentration
of 100 pg m
À3
within an agricultural region during the summer, where
both air and surface water (lakes, rivers coastal seas) have a temper-
ature of 25
o
C. Using K
aw
we can estimate the water concentration
from the air concentration assuming equilibrium has been achieved.
In the Arctic, the air concentration of g-HCH is B10 pg m
À3
(10-fold
lower), but the air and surface water temperatures in the high Arctic
during the summer are B1 1C. Again, the water concentration of
g-HCH can be estimated using K
aw
, but this time adjusted to 1 1C.
The surface water concentration in the temperate agricultural area is
calculated from the air concentrations as follows:
H for g-HCH has been measured as 0.24 Pa m
3
mol
À1
at 298 K.
21
Whereby H
0
or K
aw
¼ H/RT (T is 25 1C or B298 K)
Therefore, K
aw
¼ 0.24/8.314 Â 298 ¼ 9.69 Â 10
À5
or ln K
aw
¼ À9.24
As K
aw
¼ C
a
/C
w
, then C
w
¼ C
a
/K
aw
¼100/9.69 Â 10
À5
C
w
in the temperate agricultural region is 1.03 Â 10
6
pg m
À3
or
B1000 ng m
À3
or B1 ng L
À1
The water concentration in the Arctic is calculated in the same way
but using the C
a
for the Arctic. First, K
aw
has to be adjusted for 1 1C
(B274 K) using Equation 6.17, where:
ln K
aw
ð274 KÞ ¼ ln K
aw
ð298 KÞ À
DH
R
1
274
À
1
298

DH is 61400 J mol
À1
determined from the slope, m, in Equation 6.16
by Sahsuvar et al.
21
Note that in this study, DH actually represented
the enthalpy of water to air volatilisation, rather than the enthalpy of
air to water dissolution, and we consider 61,400 as approximate only.
Therefore:
ln K
aw
ð274 KÞ ¼ ln K
aw
ð298 KÞ À
DH
R
1
274
À
1
298

The inverse of ln K
aw
À11.4 ¼ 1.12 Â 10
À5
. Therefore, the surface
water concentration in the Arctic, attained through equilibrium par-
titioning with the air is
C
w
¼C
a
/K
aw
¼ 10 pg m
À3
/1.12 Â 10
À5
¼ 892,857 pg m
À3
or B890 ng
m
À3
or El ng L
À1
294 Chapter 6
The two water concentrations (temperate and Arctic) are similar, even
though the air concentration in the Arctic is an order of magnitude
less than temperate air. This temperature driven phenomenon that
favours chemical partitioning to surfaces is commonly known as the
‘cold condensation effect’ and has resulted in the worrying rise in
persistent organic pollutants in the polar environments.
6.4.3 Partition Maps
The rise in legislation and the concern over the use and release of
chemicals that possess physical–chemical properties that may be analo-
gous to DDT and other persistent organic pollutants such as polychlo-
rinated biphenyls (PCBs), has prompted demand for ways to rapidly
screen or assess chemicals with respect to their environmental distribution
and fate. The environmental transport, lifetime and accumulation of
organic chemicals in different compartments, such as biota, can be
quantified through the use of multi-compartment (media) chemical fate
models. It is simply not feasible to measure all chemicals of concern in a
large number of compartments over an extended period of time. Identi-
fying chemicals of concern, and the designation of the term ‘POP’ for a
chemical substance, occurs if a chemical meets the criteria specified in
Table 2. Importantly, the designation of ‘persistence’ is based on the
Table 2 Criteria used to designate a chemical substance as a persistent organic
pollutant or ‘POP’. Information from the Stockholm Convention on
POPs
31
Persistence 1. t
1/2
a
in water 4 2 months
2. t
1/2
in soil/sediments 4 2 months
3. Other evidence that the chemical is sufficiently persistent
to justify consideration
Bioaccumulation 1. BCF or Bioaccumulation Factor (BAF) in aquatic
species 4 5000
2. Log K
ow
4 5
3. Evidence of higher bioaccumulation in other species
Potential for long
range transport
1. Measured levels of the chemical in locations distant from
sources of release that are of potential concern
2. Environmental fate properties and/or model results that
demonstrate that the chemical has a potential for
long-range environmental transport
3. t
1/2
in air 4 2 days
a
t
1/2
¼half-life.
295 Environmental Organic Chemistry
exceedence of specific environmental half-lives i.e. Z6 months in soils/
sediments, Z2 months in water, Z20 days in air. The latter is partic-
ularly relevant for those chemicals, which may be released to the air and
are resistant to atmospheric degradation and/or deposition, and hence
able to undergo long-range atmospheric transport, with the potential to
contaminate remote areas. This multiple half-life approach is one adopted
by several countries including Canada,
24
whereby a chemical that exceeds
the criteria for any of these compartments may be declared persistent.
However, if the chemical is unlikely to reside in that compartment then
this may unfairly penalise a substance, because it fails the half-life
criterion for a medium into which it does not appreciably partition.
To examine this issue, Gouin et al.
32
proposed a screening level method
to allow the quick assessment of a large number of chemicals, based on
their media-specific half-lives and their partitioning characteristics. An
evaluative environmental fate model, the Equilibrium Criteria Model
(EQM), was used for this study. EQM comprised of four hypothetical
compartments air, water, soil and sediment, where octanol represented
the organic matter found in soils and sediments. Each compartment was
given a volume, in this case to represent the regional or country scale. For
example, the air volume (V
a
) was 10
14
m
3
, that is a land surface area of
100,000 m
2
, with an atmospheric height of 1000 m. 10% of this area was
considered to be covered with water to a depth of 20 m, resulting in a
water volume (V
w
) of 2 Â 10
11
m
3
. Soil was considered to have a depth of
0.1 m with the soil volume (V
soil
) calculated as 9 Â 10
9
m
3
, converted to an
equivalent volume of octanol (V
o
) according to
V
o
¼ V
soil
F Â 0:35r ð6:18Þ
where F is the fraction of organic carbon in the soil (0.02), r is the density
of soil (2.4 kg L
À1
or 2400 kg m
À3
), where 0.35 represents the constant
relating the K
oc
to K
ow
(see Equation 6.5). Similarly for sediment, the
equivalent V
o
was 3.4 Â 10
6
m
3
calculated using Equation 6.18, but with
V
sed
as 10
8
m
3
, F as 0.04 and r the same as soil. For this scenario the ratios
of the air/water/octanol volume was B650,000:1300:1. The EQM model is
a steady-state, equilibrium model into which a chemical was constantly
discharged and allowed to attain equilibrium between the various media
with no advective losses. Steady state was reached when total reactive losses
equalled the discharge rate and the model was run for 233 chemicals using
respective physical–chemical property data including K
aw
, K
ow
and K
oa
as
well as reactivity data in the various media (i.e. water, air, soil/sediment). At
equilibrium the total mass of a chemical (M, g) can be given by
M ¼ V
w
C
w
þ V
a
C
a
þ V
o
C
o
¼ C
w
ðV
w
þ K
aw
V
a
þ K
ow
V
o
Þ ð6:19Þ
296 Chapter 6
where C
o
is the chemical concentration in octanol (i.e. ‘soils/sediment’)
(g m
À3
). Note that the volume-concentration product (VxCx) gives
the mass of a chemical for a particular environmental medium. The
right-hand side of Equation 6.19 illustrates how using the partition
coefficients, the concentration of a chemical can be deduced for one
compartment with knowledge of the chemical concentration in an
adjacent compartment (e.g. K
aw
C
w
¼ C
a
). The mass fractions of a
chemical in each medium (F) are therefore
Air ðaÞ : F
a
¼ K
aw
V
a
=ðV
w
þ K
aw
V
a
þ K
ow
V
o
Þ ð6:20Þ
Water ðwÞ : F
w
¼ V
w
=ðV
w
þ K
aw
V
a
þ K
ow
V
o
Þ ð6:21Þ
Octanol ðoÞ : F
o
¼ V
o
K
ow
=ðV
w
þ K
aw
V
a
þ K
ow
V
o
Þ ð6:22Þ
Figure 4 displays the plot of log K
aw
vs. log K
ow
including points that
represent all 233 chemicals used in the study. The chemicals were selected
to represent environmental contaminants of concern and include a broad
range of different chemical classes with varying properties. Figure 4 is
effectively a partitioning map that illustrates the proportion of a chemical
within each of the compartments. The 45
o
diagonals are lines of constant
log K
oa
, as K
oa
¼ K
ow
/K
aw
(or log K
oa
¼ log K
ow
Àlog K
aw
). Lines of
constant F
a
, F
w
and F
o
were drawn using the volume ratios outlined
above for this particular study. The 1% and 99% lines divide the K
aw
/K
ow
space into regions into which chemical partitioning is predominantly into
one medium. For example, the region to the upper left of the figure is
where more than 99% of a chemical is in air, to the lower right (beyond
the 1% air line) is where more than 99% of a chemical is in the octanol
phase and to the lower left (beyond the 1% octanol line) is where more
than 99% of a chemical is in water. For chemicals that fall into these
‘areas’ then their half-lives in the respective medium will likely control
their overall persistence and the half-lives in the other media are largely
irrelevant. For example, a chemical present in the lower right of the figure,
within the octanol ‘area’, will be strongly sorbed and only degradation
data for soils/sediments is likely to be needed. Importantly, half-lives in
air are generally shorter than those in water or organic phases due to
rapid reactivity with the hydroxyl radical (OHÁ ), so that even 0.5%
partitioning to air may result in appreciable degradation with respect to
overall loss. It is therefore useful to include a line that represents the 0.1%
air. The lines corresponding to one third (33%) in each compartment,
converge where log K
ow
is 3.1 and log K
aw
is À2.74; chemicals that fall
within this area (‘A & W & O’) are truly multi-media and their half-lives
297 Environmental Organic Chemistry
for each compartment or medium would be required to determine their
overall persistence. Obviously the convergence point would change if a
different scenario was modelled, whereby the water compartment volume
was increased for example. However, out of the 233 chemicals included in
the figure, B34% had fractions 41% in each medium. If the chemicals
-10
-9
-8
-7
-6
-5
-4
-3
-2
-1
0
1
2
3
4
Log K
OW
L
o
g

K
A
W
33%
octanol
33% air
0.1% air
33%
water
Water
Air
Octanol
Water & Octanol
A & W & O
Air & Octanol
1% water
1% octanol
1% air
18
17
16
15
14
13
12
11
10
9
8
7
6
5 4 3 2 1 0 -1 -2 -3
L
o
g

K
O
A
Air
&
Water
0 1 2 3 4 5 6 7 8 9
Figure 4 K
aw
– K
ow
partitioning map with the distribution of 233 organic chemicals and
lines of equal F
a
, F
w
and F
o
; that is the chemical mass fractions in air (F
a
),
water (F
w
) and octanol (F
o
). The central region denoted ‘A&W&O’ is occupied
by chemicals which have mass fractions (41%) in all compartments of Air,
Water and Octanol and are therefore multi-media chemicals. Octanol repre-
sents organic-phases in the environment e.g. the organic carbon within soils and
sediments
From Gouin et al.
32
, courtesy of the American Chemical Society
298 Chapter 6
between the 1% and 0.1% of air are included, then B40% of the
chemicals become multi-media.
This approach of mapping chemicals into groups according to their
partitioning tendencies provides a rapid method of identifying relevant
environmental compartments where a chemical may reside. Key degra-
dation data relevant for that specific compartment can then be further
examined without the need for irrelevant data for other compartments.
6.5 CHEMICAL TRANSFORMATION AND DEGRADATION
Chemical degradation may proceed by a wide number of processes and
the reactivity of a chemical is governed by its stereochemistry (3-
dimensional structure), bond strengths and the presence of functional
groups. Both abiotic and biotic processes will transform a chemical
pollutant and the multitude of abiotic processes can be broadly grouped
under the following types of reaction: oxidation, reduction, hydrolysis
and photolysis. Indeed these generic reactions are not mutually exclu-
sive, as the generation of oxidants present in the atmosphere for exam-
ple, requires the action of sunlight on precursor molecules (e.g. the
formation of the OH radical from ozone). Several of the chlorinated
aromatic chemical groups illustrated in Figure 1 (and mentioned in
Section 6.4) are largely resistant to these transformation processes,
whereby their rates of reaction are very slow. However, even these
chemicals do degrade eventually, although their degradates may have a
similar longevity in the environment! Perhaps the fastest route of
degradation for these semi-volatile compounds is through oxidation
by the OH radical in the atmosphere, with half-lives typically on the
order of hours to days, compared to months or years in soils and
sediments. However, at any one time, the atmosphere may contain only
a very small fraction of the overall environmental ‘inventory’ so its
relevance as an important ‘sink’ for these chemicals is greatly reduced
compared to volatile organic compounds (VOCs). Nonetheless, oxida-
tion of PAHs present in the atmosphere can give rise to toxic analogues.
The reaction of higher volatility PAHs (generally the 2- to 4-ring PAHs
present predominantly in the vapour phase) with OH radicals during
daylight hours, or with nitrate (NO
3
) radicals during nighttime gives rise
to more polar hydroxy- and nitro-PAHs. The atmospheric formation of
nitro-PAHs may also occur via a daytime OH radical-initiated pathway
in the presence of NO
x
, although the formation yields of nitro-PAHs (or
nitroarenes) via this pathway are low compared to the yield of hydroxy-
PAHs.
33
Figure 5 illustrates a simplified reaction pathway of fluoran-
thene with the OH radical in the presence of NO
x,
resulting in the
299 Environmental Organic Chemistry
formation of both 3-hydroxyfluoranthene and 2-nitrofluoranthene (2-
NF). Indeed, some of the nitroarenes are strongly mutagenic and present
a risk to human health and have been reported in several recent air
sampling campaigns.
34,35
Interestingly, 2-NF is one of the major parti-
cle-associated nitro-PAHs observed in a study conducted in southern
California,
35
presumably due to its lower volatility and higher polarity
than the parent fluoranthene, resulting in its condensation/sorption to
atmospheric particles.
An important transformation process for halogenated organic com-
pounds is reductive dehalogenation, a process which largely occurs in
anoxic (oxygen free) environments, such as sediments, sewage sludges,
water-logged soils and ground-water and catalysed by the presence of
metal containing minerals, where the metal is in a low state of oxidation
e.g. zero-valent or divalent iron. The reductive potential of a halogen-
ated molecule (i.e. ‘the willingness to accept electrons from the metal
donor’) is based on many factors, not least the number and type of
halogen atoms around the molecule. In one common type of reaction the
breaking of the carbon-halogen bond (through the halogen atom ac-
cepting electrons) is followed by replacement with a H-atom (hydrogen-
olysis), resulting in the gradual ‘de-halogenation’ of the molecule. For
chlorinated solvents and chlorinated aliphatics in general, then this
OH
H
OH
NO
2
+ HONO
3-hydroxy-fluoranthene
fluoranthene
OH
NO
2
2-nitrofluoranthene
NO
2
H
OH
H
NO
2
+ H
2
O
Figure 5 The gas phase OH radical-initiated reaction of fluoranthene (a 3-ring PAH) in
the presence of NOx. The reaction results in the formation of both hydroxy- and
nitro-fluoranthene, although nitro-fluoranthene can also form from the nighttime
reaction with the NO
3
radical
Reaction scheme adapted from Arey et al.
33
300 Chapter 6
process may be driven solely by abiotic processes,
36
but for the more
stable chlorinated aromatics, reductive dechlorination is likely to be
assisted by microbial activity (or biotic processes) and is currently the
focus of much research into the biologically driven remediation of
contaminated soils and sediments.
6.6 CHEMICAL TRANSFORMATION THROUGH
PHOTOCHEMISTRY
Organic pollutants are susceptible to photochemical transformation and
degradation in both the atmosphere and in surface waters. In fact,
photochemical degradation can occur in any environmental medium
that is subject to sunlight (or more appropriately solar actinic radiation),
and includes surface reactions whereby chemicals sorbed to environ-
mental surfaces such as plant material, airborne particles and even snow
and ice are affected by sunlight. Both direct and indirect photochemistry
(the latter brought about by chemical reaction with short-lived oxidants
such as the OH radical), is of interest to the organic chemist, and can
lead to the destruction of the pollutant and/or its phototransformation.
In some cases this may lead to more persistent, or toxic, photoproducts
such as the photochemical transformation of chlorobenzenes to poly-
chlorinated biphenyls in ice
37
or the soil-sorbed photooxidation of the
organophosphorus pesticide parathion to the active toxin paraoxon.
38
The assessment of photochemistry on the fate of organic chemicals is
therefore a necessary step in risk assessment procedures (required for
pesticide registration, for example), with protocols for conducting lab-
oratory photochemical fate studies now provided by organisations like
the US-EPA, the Organisation for Economic Cooperation and Devel-
opment (OECD) and the European Chemical Bureau; the aim here is to
provide standard operating procedures to enable reproducibility in test
results and intercomparsion between different studies. These protocols
concern direct and indirect photolysis in aqueous systems, as both fresh
and marine waters are important sinks for organic pollutants. For
example, agrochemicals residing on soil and plant surfaces often end
up in surface waters, and the multitude of organic contaminants released
from waste water treatment works (WWTW) (e.g. non-ionic surfactants,
pharmaceuticals, personal care products) and their impact on receiving
waters is of growing concern.
39
However, atmospheric photochemistry
relating to both vapour and particle-bound organic contaminants is
perhaps less well studied, primarily due to the problem of maintaining a
consistent, reproducible vapour in order to conduct gas-phase photo-
chemical experiments. Nevertheless, there is a growing need to assess
301 Environmental Organic Chemistry
both direct photolysis and photooxidant chemistry to determine reac-
tion rates to establish atmospheric half-lives and hence atmospheric
transport potential – an important feature with respect to the contam-
ination of remote environments by persistent chemicals (see Table 2).
For the atmospheric chemist, much more emphasis is placed on photo-
chemistry of VOCs, which play a major role in influencing air quality, by
driving the formation of ground-level O
3
40
as well as initiating particle
formation and growth.
41
In the following sections focus will be on semi-
volatile organic contaminants and their aqueous photochemistry.
6.6.1 Light Absorption and the Beer–Lambert Law
For the environmental photodegradation of organic chemicals, direct
photolysis is an important removal process for those pollutants that
absorb light at wavelengths above 290 nm; the cut-off of solar irradia-
tion at the earth’s surface. Visible light includes those wavelengths that
cover the spectral range of 400–760 nm, whereas shorter wavelengths i.e.
290–400 nm are in the ultraviolet or UV region, and posses greater
energy than light at longer wavelengths. Hence light in the UV-region is
of most concern with respect to sunburn and skin cancers, and can
be further divided into different wavelength regions, including UV-B
(290–320 nm) and UV-A (320–400 nm).
The degree of absorption of UV and visible wavelengths (UV/vis) by
organic compounds is related to the molecular structure of the chemical,
in particular, by the presence of chromophores; structural moieties that
exhibit a characteristic UV/vis absorption spectrum. Aromatic rings and
conjugated double bonds are good examples of chromophores, but
others include double bonds containing, for example, nitrogen and
oxygen and other heteroatoms present within the carbon skeleton of
the molecule. Light absorption by organic compounds at the wave-
lengths of environmental relevance is usually associated with the delo-
calised p-electron system of double bonds (i.e. those electrons involved
in the multiple bonding of C
Q
C and C
Q
O groups, for example), rather
than electrons in sigma orbitals as part of single bonds, as the absorp-
tion maxima of these electrons generally lie at much shorter wavelengths
than the solar wavelength minimum of 290 nm. Nearly all environmen-
tal photochemistry involves the excitation of p or non-bonding electrons
(n) to higher-energy, antibonding p* orbitals, thereby destabilising the
molecule. Examples of n electrons are the non-bonding electron pairs
associated with oxygen atoms of carbonyl groups (C
Q
O) or nitrogen
atoms (C
Q
N). Chromophores consisting of a series of conjugated
carbon double bonds (C
Q
C–C
Q
C) are readily found in nature, and
302 Chapter 6
a good example are the porphyrins (of which chlorophyll is a member).
These provide useful ‘light sensitive’ systems that can harvest light
energy and in the case of chlorophyll perform the vital role of photo-
synthesis.
Absorption of light at a given wavelength (A
l
) by a solution of a
chromophoric molecule can be treated quantitatively according to the
Beer–Lambert law. The ratio of the light intensity transmitted through
the chemical solution (I
l
) to the incident light intensity (I
o,l
) can be
related to the chemical concentration (C) according to,
A
l
¼ log
I
l
I
o;l
¼ e Á C Á l ð6:23Þ
where C is expressed as molar concentration (M), e the decadic (log)
molar absorption coefficient (M
À1
cm
À1
) and l the light path length in
the chemical solution (cm). I is often expressed in units of Einstein cm
À2
s
À1
, (where an Einstein is 6.02 Â 10
23
photons or a ‘mole’ of photons)
with absolute light irradiance (expressed as Joules s
À1
m
À2
or Watts
m
À2
) measured using a chemical actinometer for a specified wavelength
range.
6.6.2 Photolysis in Aqueous Systems
Light absorbance studies can be conducted using a UV/vis spectropho-
tometer programmed to irradiate a solution at individual wavelengths
over part, or all, of the solar spectrum. Quartz-glass cuvettes (l ¼ 1 cm)
are usually employed which hold the chemical solution and a reference
solution (i.e. typically the solvent but without the chemical to assess the
absorbance artefacts of the holding solvent). Water is the solvent used
for environmental fate studies, but apolar or monopolar organic com-
pounds (including many pesticides) are only sparingly soluble in water
so an organic solvent – water solution is often used, where the organic
solvent is strongly polar and water-miscible such as methanol or aceto-
nitrile. Figure 6 shows the spectral absorbance of chlorpyrifos (a cur-
rently used organophosphorus insecticide) in pure methanol between the
wavelengths 200–400 nm. Chlorpyrifos displays several absorbance
maxima, but within the UV-B/UV-A range of the solar spectrum the
maximum absorbance occurs at 288 nm and e288 nm can be calculated
by rearranging Equation 6.23 to:
e
288 nm
¼
A
288 nm
C Á l
ð6:24Þ
303 Environmental Organic Chemistry
From Figure 6, A
288 nm
¼ 0.49 and was generated with C as B0.1 mM
(or 1 Â 10
À4
M) and l ¼ 1 cm, the value of e
288 nm
is therefore:
e
288 nm
¼
0:49
10
À4
 1
¼ 4900 M
À1
cm
À1
ð6:25Þ
Values of l
max
and e
max
are useful to assess whether a compound might
absorb ambient light and therefore be susceptible to environmental pho-
todegradation. Values of e however need to be calculated for each wave-
length if full quantification of photochemical processes is required. Indeed
for chlorpyrifos, significant absorbance occurs at wavelengths 4290 nm
suggesting that photodegradation is worth considering with respect to its
environmental fate. It is worth noting that the solvent in which the
chemical resides may have a strong influence on the absorption spectrum,
and is important when trying to replicate environmental conditions for a
chemical with a low aqueous solubility. It is therefore relatively common
practice to replicate photochemical experiments using a number of solvent-
water mixtures to assess the solvent effect on the spectral absorbance.
Indeed, OECD guidelines with respect to aqueous photodegradation
studies on compounds with low solubility, recommend that co-solvents
λ
max
=288nm
Chlorpyrifos
N
O
Cl
Cl
Cl
P
S
OCH
2
CH
3
OCH
2
CH
3
UV-region
of natural sunlight
Wavelength(nm)
Figure 6 Spectral absorbance of the insecticide chlorpyrifos (in methanol) over UV
wavelengths. For the environmentally relevant range of the UV spectrum (UV-
A/B), l
max
occurs at 288 nm, with significant absorbance at higher wavelengths
(to 310 nm), suggesting natural sunlight is capable of inducing phototransfor-
mation (thanks to J. Weber, Lancaster University, for generating the absorb-
ance spectrum)
304 Chapter 6
should not comprise more than 1% by volume of the test solution.
Furthermore, the co-solvent must not solvolyse the test chemical, must
not absorb in the 290–800 nm region, and must not be a photosensitiser
(that is promote chemical change through indirect photolysis due to
exchange of molecular energy with the test chemical). To this end, aceto-
nitrile and methanol (MeOH) are the co-solvents of choice (e.g. aqueous
solutions comprising 99.5% H
2
O/0.5% CH
3
CN), but not acetone because
of its strong photosensitizing effect.
Natural waters contain dissolved organic carbon (DOC) and also vary
in pH (typically between pH 5 and 8). Both DOC and pH can have a
marked effect on the photochemical degradation of organic pollutants
and for realistic photochemical studies to be undertaken both factors need
to be taken into account, particularly for ionisable chemicals that may
dissociate in water depending on their acid dissociation constant (pKa)
and the pH of the water. DOC comprises the principal light absorbing
component in surface waters (comprising humic and fulvic acids) that
provide the natural colouration of waters arising in organic-rich environ-
ments. Direct photochemical reactions can be slowed by the shielding
effect of DOC, but additionally sensitised reactions may occur by indirect
light-induced reactions of the dissolved material. One example of this type
of light-induced reaction with DOC, is the possible coupling reactions of
triclosan with humic matter, to form insoluble particles.
42
Triclosan is a
relatively common anti-microbial agent added to hand-washes, tooth-
paste and other personal care products and is frequently detected in
surface waters throughout Europe and North America. Direct photo-
transformation is responsible for the majority of triclosan loss in surface
waters
43
and photobyproducts include 2,4-dichlorophenol and 2,8-
dichlorodibenzo-p-dioxin.
42
Only the anion of triclosan is susceptible to
significant phototransformation and as its pKa is 7.9 (weak acid), then the
anion will predominate in water with a pH of 48. The photochemical
reaction pathway is illustrated in Figure 7 and provides a useful example
of photochemistry that is pH dependent and where DOC appears to
influence the reaction by-products.
6.6.3 Photochemistry of Brominated Flame Retardants (BFRs)
Brominated flame retardants (BFRs) are an interesting and important
group of chemicals that are widely incorporated into plastics, foams,
electrical items and furnishings to reduce the risk of fire. Indeed, it is
likely that the polyurethane foam used in an upholstered chair in which
you maybe sitting, will have been treated with a BFR in order to
conform to fire-safety standards. However, their widespread use, release
305 Environmental Organic Chemistry
into the environment and occurrence in wildlife and human blood has
resulted in growing concern about these groups of chemical.
44,45
BFRs function by decomposing under heat to give rise to Br
d
radicals
that react with hydrocarbons (flammable gases), given off by the burning
substance, to form HBr molecules. These, in turn, ‘mop-up’ high energy
OH
d
and H
d
radicals formed as part of the combustion chain reaction,
thereby effectively retarding or slowing the combustion process. The
effectiveness of a BFR is therefore dependent on the quantity of Br
d
radicals that can be released and the control of their release. Ideally, for
the latter, the BFR should decompose at a lower temperature than that
of the polymer in which it is incorporated and this will determine,
among other things, the type of BFR used in a particular application.
45
Two important BFRs are the polybrominated diphenyl ethers
(PBDEs) and tetrabromobisphenol A (TBBPA) and their respective
structures are presented in Figure 8. PBDEs are utilised as additives for
treating plastics and polymers used within electronic components and
Triclosan
O
OH
Cl Cl
Cl
pKa = 7.9
O
O
-
Cl Cl
Cl
Cl
Cl
OH
O
O
Cl Cl
2,4-DCP
2,8-DCDD
DOC
hv
hv
hv
Coupling reaction
with humic material
Triclosan-anion
Figure 7 Direct photochemical reaction pathway of Triclosan (5-chloro-2-(2,4-di-
chlorophenoxy)phenol) in natural water (3–100 mM of Triclosan in pH-
buffered solutions), irradiated with a Hg-vapour lamp. Only the triclosan
phenolate anion (present in water at pH 48) is susceptible to significant
photochemical transformation and will also react through indirect photolysis
(not shown) with singlet oxygen (
1
O
2
) and OH radicals to form 2,4-dichloro-
phenol (2,4-DCP). The photoproduct 2,8-dichlorodibenzo-p-dioxin (2,8-
DCDD) belongs to a notoriously persistent group of chemicals commonly
referred to as ‘dioxins’
From Latch et al.
42
courtesy of SETAC press
306 Chapter 6
electrical equipment in general, and are also used extensively as additives
in textiles and flexible foams, whereby they are dissolved in the polymer
before it is formed into shape or blown into its foam structure. As a
result, PBDEs, will, over time, volatilise from the equipment or furnish-
ing into which they have been added. TBBPA, on the other hand, is
primarily used as a reactive flame retardant i.e. it is covalently bound
into mainly epoxy and polycarbonate resins used in the manufacture of
printed circuit boards within electronic equipment.
6.6.3.1 Demand for BFRs. PBDEs are grouped into homologues ac-
cording to the number of bromine atoms around the phenyl rings and are
available commercially as three different formulations; pentaBDE, oct-
aBDE and decaBDE, whereby the penta- and octaBDEcontain between 10
and 20 individual congeners and the decaBDE formulation largely com-
prising of the single congener, decabrominated diphenyl ether. Worldwide
demand of PBDEs is high, and is estimated to be 7500 t for pentaBDE,
3760 t for octaPBDE and 56100 t for decaBDE for 2001,
46
although
quantities of the pentaBDE and octaPDE are likely to change following a
ban by the European Union and a voluntary phase-out by one of the main
industrial producers in the US. Concern arises due to PBDE occurrence in
human blood and breastmilk, with evidence of increasing PBDE levels in
wildlife.
44
The physical–chemical properties of the PBDEs are analogous to
‘legacy’ persistent organic pollutants such as polychlorinated biphenyls
(PCBs), previously used in the electrical industry. For example, PBDEs are
semi-volatile (although the decabrominated congener is considered non-
volatile at ambient temperatures) with log K
ow
values of 5.9–6.2 for tetra-
BDE, 6.5–7.0 for pentaBDE, 8.4–8.9 for octaBDE and 10 for decaBDE;
46
evidence of their propensity for movement in the environment and ability
to strongly partition to fats/lipids.
It is estimated that worldwide demand for TBBPA in 2001 was some
120,000 tonnes
47
and concern over this chemical (and related phenols) has
arisen due to its occurrence in sewage sludge, aquatic sediments and fish.
PBDE structure
O
yBr xBr
TBBPA
CH
3
CH
3
Br
OH
Br
Br
HO
Br
Figure 8 Generic structure of the polybrominated diphenyl ether (PBDE) and the
structure of tetrabrominated bisphenol-A (TBBPA). Note the x and y on the
PBDE structure represent the number of bromine atoms around each phenyl
ring (where x ¼ 1–5 and y ¼ 1–5). The maximum number of 5 bromine atoms
on each ring results in the fully brominated, decabrominated diphenyl ether
307 Environmental Organic Chemistry
6.6.3.2 PBDE and TBBPA Photochemistry. For aryl-halides, the
bromine-carbon bond is not as strong as the chorine-carbon bond, with
a typical bond-dissociation energy of the bromine-carbon bond of 301
kJ mol
À1
compared to 360 kJ mol
À1
for the chlorine-carbon bond.
48
Therefore, unlike PCBs, many PBDEs are more susceptible to loss of the
halogen atoms and photochemical decomposition has been recognised
as an important route for both debromination and transformation for
various PBDE congeners present in the wider environment. Several
studies have investigated the photochemical degradation of PBDEs
46,49
to determine rates of degradation and identify photodegradation by-
products in aqueous solutions under simulated light conditions. Figure 9
shows the absorption spectra (e) of seven PBDE congeners dissolved in
tetrahydrofuran (several of the higher brominated congeners are only
sparingly soluble in MeOH/H
2
O) and exposed to a UV-light source in
the study of Eriksson et al.
46
Clearly the higher brominated congeners
absorb light at longer wavelengths, possessing higher l
max
values than
less brominated congeners. As such, the rate of degradation of PBDEs
by UV light in the sunlight region was found to be dependent on the
290 300 310 320 330 340 350
0
0
0.5
1.0
1.5
2.0
2.5
J
s
-
1
c
m
-
2
λ (nm)
(×10
-4
)
500
1000
1500
2000
2500
3000
ε

(
c
m
-
1

M
-
1
)
8
1
2
3
5
6
7
4
Figure 9 Absorbance spectra (expressed as e, the molar absorbance coefficient) of seven
PBDE congeners. The line numbers ar: (1) BDE-209; (2) BDE-206; (3)
BCDE-203; (4) BDE-183; (5) BDE-155; (6) BDE-85; (7) BDE-77; line 8
represents the UV light irradiance in units of J s
À1
cm
À2
(or W cm
À2
)
From Eriksson et al.
46
courtesy of the American Chemical Society
308 Chapter 6
degree of bromination, whereby the lower brominated congeners gen-
erally degraded at a much slower rate than that of the higher brominated
congeners. For example, the observed first order rate constant (k) for the
photodecomposition of BDE-47 (a tetrabrominated diphenyl ether) in
MeOH/H
2
O solution was 0.07 Â 10
5
s
À1
compared to 40 Â 10
5
s
À1
for
BDE-209 (the decabrominated diphenyl ether). The relatively slow rate
of reaction of BDE-47 (approximately 600-fold less than BDE-209) can
be largely attributed to its lower absorbance of light at longer wave-
lengths, which in turn may help to explain the prevalence of PBD-47 in
environmental samples. Interestingly, Eriksson et al.
46
observed that the
decaBDE decomposed to lower brominated diphenyl ethers and also
tentatively identified additional photodegradation by-products includ-
ing methoxylated polybrominated dibenzofurans through interpretation
of mass spectra following analysis of the photolysis solution by GC-MS.
A similar aqueous photochemistry study on TBBPA
47
has found
much faster rates of transformation for this chemical relative to the
PBDEs. However, the rate was dependent on the pH of the solution,
with phototransformation favouring the anion of TBBPA, present at a
significant fraction when the pH of the test solution was 48 (the pKa of
TBBA is B7.5–8.5). At pH 10, l
max
and e
max
were 310 nm and 9170
cm
À1
M
À1
respectively, compared to 290 nm and B2000 cm
À1
M
À1
at
pH 5.5, illustrating that at the higher pH the TBBA-anion is absorbing
strongly at a higher wavelength compared to TBBPA and therefore
more likely to be photodegraded under natural sunlight. The value of k
for the photodecomposition of TBBPA in an aqueous solution at pH 10
was measured as 0.7 Â 10
3
s
À1
, compared to 0.033 Â 10
À3
s
À1
at pH 5.5,
and the photodegradates included a number of bromophenols and
alkylated bromophenols.
6.7 CONCLUSIONS
Knowledge of the partitioning properties of organic contaminants is
fundamental to understanding their environmental distribution and
hence fate. For many organic chemicals that pose a threat to the
environment, there is a lack of robust temperature-dependent partition
coefficients, and in many instances these have to be estimated either
from other partitioning descriptors or modelled from the molecular
properties of the chemical. Partition ‘maps’ provide a useful way to
visualise the environmental distribution of a wide range of chemical
classes, and to identify those relevant media where a chemical may
reside. Increasingly the results from multi-media chemical fate models
309 Environmental Organic Chemistry
are displayed in this way and partition maps will likely provide a useful
tier for chemical risk assessment in the future.
Unlike the older ‘legacy’ POPs, such as DDT and PCBs, many current
chemicals used in agriculture, industry and for domestic purposes, are
generally more susceptible to degradation processes once present in the
environment (although, ironically, the persistent nature of DDT can be
attributed to its biological degradate p,p
0
-DDE). In some instances these
degradates may be more persistent and/or harmful to the environment
than the parent chemicals. The photolytic degradation of Triclosan and
certain BFRs are a case in point. Interestingly, a recent review on
pesticide-degradates highlighted their higher frequency of detection over
the parent compounds in surface water sampled across the US.
50
These
pesticide-degradates typically had longer half-lives and lower log K
oc
values than the parent pesticides, making them relatively long-lived and
more mobile in the environment. Future research efforts will be required
to understand the fate of these chemicals and the threat they pose to
both humans and the environment.
6.8 QUESTIONS
(i) A pesticide has an experimentally determined K
d
value of 5.6,
calculate its K
oc
value assuming the soil has a 2% organic carbon
content. What type of polymeric material comprises a large
proportion of the organic carbon fraction in soil? Describe how
you could operationally separate its base-soluble fraction?
(ii) The Henry’s Law constant for a pesticide at 25
o
C has been
experimentally determined as 0.008 Pa m
3
mol
À1
. Calculate K
aw
(dimensionless Henry’s Law constant)? If this pesticide has a log
K
ow
2.9, which environmental compartment is the chemical likely
to reside in (use the partition map of Figure 3 to help with your
answer)?
(iii) The pesticide outlined in Question (i) and (ii) does not absorb
sunlight in aqueous solution, however upon dissociation its anion
strongly absorbs wavelengths 4300 nm. If this pesticide has a
pKa of 6 and is present in surface waters with a pH B8, describe
the probable fate of this chemical.
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313 Environmental Organic Chemistry
CHAPTER 7
Biogeochemical Cycling of Chemicals
ROY M. HARRISON
Division of Environmental Health & Risk Management, School of
Geography, Earth & Environmental Sciences, University of Birmingham,
Edgbaston, Birmingham B15 2TT, UK
7.1 INTRODUCTION: BIOGEOCHEMICAL CYCLING
The earlier chapters of this book have followed the traditional sub-
division of the environment into compartments (e.g. atmosphere, oceans,
etc.). While the sub-divisions accord with human perceptions and have
certain scientific logic, they encourage the idea that each compartment is
an entirely separate entity and that no exchanges occur between them.
This, of course, is far from the truth. Important exchanges of mass and
energy occur at the boundaries of the compartments and many processes
of great scientific interest and environmental importance occur at these
interfaces. A physical example is that of transfer of heat between the
ocean surfaces and the atmosphere, which has a major impact upon
climate and a great influence upon the general circulation of the atmos-
phere. A chemically based example is the oceanic release of dime-
thylsulfide to the atmosphere, which may, through its decomposition
products, act as a climate regulator (see Chapters 2 and 4).
Pollutants emitted into one environmental compartment will, unless
carefully controlled, enter others. Figure 1 illustrates the processes
affecting a pollutant discharged into the atmosphere.
1
As mixing proc-
esses dilute it, it may undergo chemical and physical transformations
before depositing in rain or snow (wet deposition) or as dry gas or
particles (dry deposition). The deposition processes cause pollution of
land, freshwater, or the seas, according to where they occur. Similarly,
pollutants discharged into a river will, unless degraded, enter the seas.
Solid wastes are often disposed into a landfill. Nowadays these are
314
carefully designed to avoid leaching by rain and dissemination of
pollutants into groundwaters, which might subsequently be used for
potable supply. In the past, however, instances have come to light where
insufficient attention was paid to the potential for groundwater con-
tamination, and serious pollution has arisen as a result.
Another important consideration regarding pollutant cycling is that of
degradability, be it chemical or biological. Chemical elements (other than
radioisotopic forms) are, of course, non-degradable and hence once dis-
persed in the environment will always be there, although they may move
between compartments. Thus, lead, for example, after emission from
industry or motor vehicles, has a rather short lifetime in the atmosphere,
but upon deposition causes pollution of vegetation, soils, and waters.
2
On a
very long timescale, lead in these compartments will leach out from soils
and transfer to oceans, where it will concentrate in bottom sediments.
Some chemical elements undergo chemical changes during environmental
cycling, which completely alter their properties. For example, nitrate added
to soil as fertilizer can be converted to gaseous nitrous oxide by biological
denitrification processes. Nitrous oxide is an unreactive gas with a long
atmosphere lifetime, which is destroyed only by breakdown in the strato-
sphere. As will be seen later, nitrogen in the environment may be present in
a wide range of valence states, each conferring different properties.
Some chemical compounds are degradable in the environment. For
example, methane (an important greenhouse gas) is oxidized via carbon
Dry
transformations
Air
concentrations
Transport
and diffusion
Wet
transformations
Scavenging
Scavenging
Wet
deposition
Dry
deposition Natural Manmade
Total emissions
Initial
mixing
Figure 1 Schematic diagram of the atmospheric cycle of a pollutant
1
(Reprinted from Environmental Science and Technology by permission of the
American Chemical Society.)
315 Biogeochemical Cycling of Chemicals
monoxide to carbon dioxide and water. Thus, although the chemical
elements are conserved, methane itself is destroyed and were it not
continuously replenished would disappear from the environment. The
breakdown of methane is an important source of water vapour in the
stratosphere, illustrating another, perhaps less obvious, connection be-
tween the cycles of different compounds.
Degradable chemicals that cease to be used will disappear from the
environment. Polychlorinated biphenyls (PCBs) are no longer used
industrially to any significant degree, having been replaced by more
environmentally acceptable alternatives. Their concentrations in the
environment are decreasing, although because of their slow degradabil-
ity (i.e. persistence), it will take many years before their levels decrease
below analytical detection limits.
The transfer of an element between different environmental compart-
ments, involving both chemical and biological processes, is termed
biogeochemical cycling. The biogeochemical cycles of the elements lead
and nitrogen will be discussed later in this chapter.
7.1.1 Environmental Reservoirs
To understand pollutant behaviour and biogeochemical cycling on a
global scale, it is important to appreciate the size and mixing times of the
different reservoirs. These are given in Table 1. The mixing times are a
very approximate indication of the timescale of vertical mixing of the
reservoir.
3
Global mixing can take very much longer as this involves
some very slow processes. These mixing times should be treated with
considerable caution as they oversimplify a complex system. Thus, for
example, a pollutant gas emitted at ground level mixes in the boundary
layer (approximately 0–1 km altitude) on a timescale typically of hours.
Mixing into the free troposphere (1–10 km) takes days, while mixing
into the stratosphere (10–50 km) is on the timescale of several years.
Thus, no one timescale describes atmospheric vertical mixing, and the
same applies to other reservoirs. Such concepts are useful, however,
Table 1 Size and vertical mixing of various reservoirs (from Brimblecombe
3
)
Mass (kg) Mixing time (years)
Biosphere 4.2 Â 10
15
60
Atmosphere 5.2 Â 10
18
0.2
Hydrosphere 1.4 Â 10
21
1600
Crust 2.4 Â 10
22
43 Â 10
7
Mantle 4.0 Â 10
24
4 10
8
Core 1.9 Â 10
24
316 Chapter 7
when considering the behaviour of trace components. For example, a
highly reactive hydrocarbon emitted at ground level will probably be
decomposed in the boundary layer. Sulfur dioxide, with an atmospheric
lifetime of days, may enter the free troposphere but it is unlikely to enter
the stratosphere. Methane, with a lifetime of several years, extends
through all of the three regions.
It should be noted from Table 1 that the atmosphere is a much smaller
reservoir in terms of mass than the others. The implication is that a given
pollutant mass injected into the atmosphere will represent a much larger
proportion of total mass than in other reservoirs. Because of this, and
the rather rapid mixing of the atmosphere, global pollution problems
have become serious in relation to the atmosphere before doing so in
other environmental media. The converse also tends to be true, that once
emissions into the atmosphere cease, or diminish, the beneficial impact is
seen on a relatively short timescale. This has been seen in relation to
lead, for instance, where lead in Antarctic ice (derived from snow) has
shown a major decrease resulting from diminishing emissions from
industry and use of leaded petrol
4
(Figure 2). Improved air quality in
relation to CFCs will take longer to achieve because of the much longer
atmospheric lifetimes (4100 years) of some species (see Chapter 1).
7.1.2 Lifetimes
A very useful concept in the context of pollutant cycling is that of the
lifetime or residence time of a substance in a given reservoir. We can
think in terms of substances having sources, magnitude S, and sinks,
magnitude R. At equilibrium
R ¼ S
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

l
e
a
d

(
p
g
/
g
)
100
0
1800 1900 2000
Date of deposition of snow or ice
LEAD
Figure 2 Changes in lead concentrations in snow/ice deposited in central Greenland from
1773 to 1992
(Adapted from Candelone et al.
4
)
317 Biogeochemical Cycling of Chemicals
An analogy is with a bath; the inflow from a tap (S) is equal to the outflow
(R) when the bath is full. An increase in S is balanced by an increase in R.
If the total amount of substance A in the reservoir (analogy ¼ mass of
water in the bath) is A, then the lifetime, t is defined by
t ¼
A ðkgÞ
S ðkg s
À1
Þ
ð7:1Þ
In practical terms, the lifetime is equal to the time taken for the
concentration to fall to 1/e (where e is the base of natural logarithms)
of its initial concentration, if the source is turned off. If the removal
mechanism is a chemical reaction, its rate may be described as follows
R
0
¼
d½AŠ
dt
¼ k½AŠ ð7:2Þ
(In this case d[A]/dt describes the rate of loss of A if the source is
switched off; obviously with the source on, at equilibrium d[A]/dt¼0.)
The latter part of Equation (7.2) assumes first order decay kinetics, i.e.
the rate of decay is equal to the concentration of A, termed [A],
multiplied by a rate constant, k. As discussed later this is often a
reasonable approximation.
Taking Equation (7.1) and dividing both numerator and denominator
by the volume of the reservoir, allows it to be rewritten in terms of
concentration. Thus
t ¼
½AŠ ðkg m
À3
Þ
S
0
ðkg m
À3
s
À1
Þ
ð7:3Þ
since S
0
¼ R
0
t ¼
½AŠ
k½AŠ
¼ k
À1
ð7:4Þ
Thus the lifetime of a constituent with a first order removal process is
equal to the inverse of the first order rate constant for its removal.
Taking an example from atmospheric chemistry, the major removal
mechanism for many trace gases is reaction with hydroxyl radical, OH.
Considering two substances with very different rate constants
5
for this
reaction, methane and nitrogen dioxide
CH
4
þ OH -CH
3
þ H
2
O (7.5)
Àd
dt
½CH
4
Š ¼ k
2
½CH
4
Š ½OHŠ k
2
¼ 6:2 Â 10
À15
cm
3
molec s
À1
ð7:6Þ
318 Chapter 7
NO
2
þ OH ! HNO
3
k
2
¼ 1:4 Â 10
À11
cm
3
molec s
À1
ð7:7Þ
Making the crude assumption of a constant concentration of OH
radical
6
(more justifiable for the long-lived methane, for which fluctu-
ations in OH will average out, than for short-lived nitrogen dioxide)
Àd
dt
½CH
4
Š ¼ k
2
½CH
4
Š ½OHŠ
¼k
0
1
½CH
4
Š
where k
0
1
¼ k
2
[OH]
Worked example
What are the atmospheric lifetimes of CH
4
and NO
2
if the diurnally
averaged concentration of OH radical is 1 Â 10
6
molec cm
À3
?
k
0
1
¼6:2 Â 10
À15
 1  10
6
¼6:2 Â 10
À9
s
À1
Then from Equation (7.4)
t ¼k
À1
¼ð6:2  10
À9
Þ
À1
s
¼5:1 years for CH
4
By analogy, for nitrogen dioxide, the lifetime
t ¼ 20 h
This general approach to atmospheric chemical cycling has proved
useful in many instances. For example, measurements of atmospheric
concentration, [A], for a globally mixed component may be used to
estimate source strength, since
S
0
¼ R
0
¼
Àd½AŠ
dt
¼ k
2
½AŠ½OHŠ
and
S ¼ S
0
 V
where V is the volume of atmosphere in which the component is mixed.
Source strengths estimated in this way, for example, for the compound
methyl chloroform, CH
3
CCl
3
, known to destroy stratospheric ozone,
may be compared with known industrial emissions to deduce whether
natural sources contribute to the atmospheric burden.
319 Biogeochemical Cycling of Chemicals
7.1.2.1 Influence of Lifetime on Environmental Behaviour. Some
knowledge of environmental lifetimes of chemicals is very valuable in
predicting their environmental behaviour. In relation to the atmosphere,
there is an interesting relationship between the spatial variability in the
concentrations of an atmospheric trace species and its atmospheric
lifetime.
3
Compounds such as methane and carbon dioxide with a long
lifetime with respect to removal from the atmosphere by chemical
reactions or dry and wet deposition (see Section 7.2 of this chapter)
show little spatial variability around the globe, as their atmospheric
lifetime (several years) exceeds the timescale of mixing of the entire
troposphere (of the order of a year). On the other hand, for a short-lived
species such as nitrogen dioxide, removal by chemical means or dry or
wet deposition occurs much more quickly than atmospheric mixing and
hence there is very large spatial variability, with concentrations some-
times exceeding 100 ppb in urban areas, while remote atmosphere
concentrations can be a the level of a few parts per trillion. By analogy,
short-lived species also show a much greater hour-to-hour and day-to-
day variation at a given measuring point than long-lived species for
which local sources impact only to a modest degree on the existing
background concentration.
This illustration using the atmosphere can be taken somewhat further
in relation to other environmental media. Lifetimes of highly soluble
species such as sodium and chloride in the oceans are long compared to
the mixing times and therefore variations in salinity across the world’s
oceans are relatively small (see Chapter 4). In contrast, where soils are
concerned, mixing times will generally far exceed lifetimes and extreme
local hot spot concentrations can be found where soils have become
polluted.
Lifetime also influences the way in which we study the environmental
cycles of pollutants. In the case of reactive atmospheric pollutants, it is
the reaction rate, or rate of dry or wet deposition, which determines the
lifetime. We are therefore concerned mainly with the rates of these
processes in determining the atmospheric cycle. In the case of longer-
lived species, such as persistent organic compounds like PCBs and
dioxins, chemical reaction rates are rather slow and these compounds
can approach equilibrium between different environmental media such
as the atmosphere and surface ocean or the atmosphere and surface soil,
with evaporation exceeding deposition during warmer periods and wet
and dry depositions replacing the contaminant in the soils or oceans in
cooler weather conditions. Both the kinetic approach dealing with
reaction rates and the thermodynamically based approach considering
partition between environmental media will be introduced in this
320 Chapter 7
chapter. In general the kinetic or reaction rate approach will be most
appropriate to the study of short-lived reactive substances, while the
equilibrium approach will be more applicable to long-lived substances.
7.2 RATES OF TRANSFER BETWEEN ENVIRONMENTAL
COMPARTMENTS
7.2.1 Air–Land Exchange
The land surface is an efficient sink for many trace gases. These are
absorbed or decomposed on contact with plants or soil surfaces. Plants
can be particularly active because of their large surface area and ability
to absorb water-soluble gases. The deposition process is crudely de-
scribed by the deposition velocity, n
d
,
n
d
ðcms
À1
Þ ¼
Flux ðmg m
À2
s
À1
Þ
Atmospheric concentration ðmg m
À3
Þ
The term flux is analogous to a flow of material, in this case expressed as
micrograms of substance depositing per square metre of ground surface
per unit time. In the case of rough surfaces the square metre of area
refers to the area of hypothetical horizontal flat surface beneath the true
surface rather than the sum of the area of all the rough elements such as
plant leaves, which make up the true surface.
Since the deposition process itself causes a gradient in atmospheric
concentration, n
d
is defined in relation to a reference height, usually 1 m,
at which the atmospheric concentration is measured. For reasons de-
scribed later, n
d
is not constant for a given substance, but varies
according to atmospheric and surface conditions. However, some typ-
ical values are given in Table 2, which exemplify the massive variability.
Table 2 Some typical values of deposition velocity
Pollutant Surfaces Deposition velocity (cm s
À1
)
SO
2
Grass 1.0
SO
2
Ocean 0.5
SO
2
Soil 0.7
SO
2
Forest 2.0
O
3
Dry grass 0.5
O
3
Wet grass 0.1
O
3
Snow 0.1
HNO
3
Grass 2.0
CO Soil 0.05
Aerosol (42.5 mm) Grass 0.1
321 Biogeochemical Cycling of Chemicals
For some trace gases, for example, nitric acid vapour, dry deposition
represents a major sink mechanism. In this case the process may have a
major impact upon atmospheric lifetimes.
Worked example
Dry deposition is frequently the main sink for ozone in the rural
atmospheric boundary layer. What is the lifetime of ozone with
respect to this process?
Assuming a typical dry deposition velocity of 1 cm s
À1
and a bound-
ary layer height of 1000 m, (H),
Àd
dt
½O
3
Š ðmg m
À3
s
À1
Þ ¼
Fluxðmg m
À2
s
À1
Þ
Mixing depth ðmÞ
¼
n
d
 ½O
3
Š
H
¼k½O
3
Š
where k ¼ n
d
/H
By analogy with Equation (7.4),
t ¼
H
n
d
¼
1000
0:01 s
¼28 h
Thus taking the boundary layer as a discrete compartment, the
lifetime of ozone with respect to dry deposition is around 1 day. The
lifetime in the free troposphere (the section of the atmosphere above the
boundary layer) is longer, being controlled by transfer processes in and
out, and chemical reactions. The stratosphere lifetime of ozone is
controlled by photochemical and chemical reaction processes.
Dry deposition processes are best understood by considering a resist-
ance analogue. In direct analogy with electrical resistance theory, the
major resistances to deposition are represented by three resistors in
series. Considering the resistances in sequence, starting well above the
ground, these are as follows:
(i) r
a,
the aerodynamic resistance describes the resistance to transfer
downwards towards the surface through normally turbulent air;
322 Chapter 7
(ii) r
b
, the boundary layer resistance describes the transfer through a
laminar boundary layer (approximately 1 mm thickness) at the
surface;
(iii) r
s
, the surface (or canopy) resistance is the resistance to uptake by
the surface itself. This can vary enormously, from essentially zero
for very sticky gases such as HNO
3
vapour, which attach irre-
versibly to surfaces, to very high values for gases of low water
solubility, which are not utilised by plants (e.g. CFCs).
Since these resistances operate essentially in series, the total resistance,
R, which is the inverse of the deposition velocity, is equal to the sum of
the individual resistances.
R ¼
1
n
d
¼ r
a
þ r
b
þ r
s
ð7:8Þ
Some trace gases have a net source at the ground surface and diffuse
upwards; an example is nitrous oxide.
Whether the flux is downward or upward, it is driven by a concen-
tration gradient in the vertical, dc/dz. The relationship between flux, F,
and concentration gradient is
F ¼ K
z
dc
dz
where K
z
is the eddy diffusivity in the vertical (a measure of the
atmospheric conductance). Fluxes, and thus deposition velocities, can
be estimated by measurement of a concentration gradient simultane-
ously with the eddy diffusivity.
7
It is usually assumed that trace gases
transfer in the same manner as sensible heat (i.e. convective heat
transfer, not radiative or latent heat) or momentum. Thus, the eddy
diffusivity for either of these parameters is measured usually from
simple meteorological variables (gradients in temperature and wind
speed).
A few substances are capable of showing both upward and downward
fluxes. An example is ammonia. Ammonium in the soil, NH
4
1
, is in
equilibrium with ammonia gas, NH
3(g)
NH
4
1
þ H
2
O "NH
3(g)
þ H
3
O
1
(7.9)
when atmospheric concentrations of ammonia exceed equilibrium
concentrations at the soil surface (known as the compensation point),
the net flux of ammonia is downwards. When atmospheric concen-
trations are below the equilibrium value, ammonia is released into the
air.
8
323 Biogeochemical Cycling of Chemicals
7.2.2 Air–Sea Exchange
The oceans cover some two-thirds of the Earth’s surface and conse-
quently provide a massive area for exchange of energy (climatologically
important) and matter (an important component of geochemical cycles).
The seas are a source of aerosol (i.e. small particles), which transfer to
the atmosphere. These will subsequently deposit, possibly after chemical
modification, either back in the sea (the major part) or on land (the
minor part). Marine aerosol comprises largely unfractionated seawater,
but may also contain some abnormally enriched components. One
example of abnormal enrichment occurs on the eastern coast of the
Irish Sea. Liquid effluents from the Sellafield nuclear fuel reprocessing
plant in west Cumbria are discharged into the Irish Sea by pipeline. At
one time, permitted discharges were appreciable and as a result radio-
isotopes such as
137
Cs and several isotopes of plutonium have accumu-
lated in the waters and sediments of the Irish Sea. A small fraction of
these radioisotopes were carried back inland in marine aerosol and
deposited predominantly in the coastal zone.
9
While the abundance of
137
Cs in marine aerosol was reflective only of its abundance in seawater
(an enrichment factor – see Chapter 4 – of close to unity), plutonium was
abnormally enriched due to selective incorporation of small suspended
sediment particles in the aerosol. This has manifested itself in enrich-
ment of plutonium in soils on the west Cumbrian coast,
10
shown as
contours of
2391240
Pu deposition (pCi cm
À2
) to soil in Figure 3.
The seas may also act as a receptor for depositing aerosol. Deposition
velocities of particles to the sea are a function of particle size, density,
and shape, as well as the state of the sea. Experimental determination of
aerosol deposition velocities to the sea is almost impossible and has to
rely upon data derived from wind tunnel studies and theoretical models.
The results from two such models appear in Figure 4, in which particle
size is expressed as aerodynamic diameter, or the diameter of an aero-
dynamically equivalent sphere of unit specific gravity.
11,12
If the air-
borne concentration in size fraction of diameter d
i
is c
i
, then
Total Flux ¼
X
i
n
d
ðd
i
Þc
i
where v
d
(d
i
) is the mean value of deposition velocity appropriate to the
size fraction d
i
. Measurements show that while most of the lead, for
example, is associated with small, sub-micrometre particles, the larger
particles compose the major part of the flux.
Airborne concentrations of particulate pollutants are not uniform
over the sea. The spatial distribution of zinc over the North Sea
13
324 Chapter 7
averaged over a number of measurement cruises appears in Figure 5.
Spatial patterns of other metals and many artificial pollutants are
similar, reflecting the impact of land-based source regions, with concen-
trations falling towards the north and centre of the sea.
IRISH
SEA
10 km
Figure 3 Concentrations of plutonium in soils of West Cumbria (
239 1 240
Pu to 15 cm
depth; pCi cm
À2
). The point marked S indicates the position of the Sellafield
reprocessing works
(From Cawse
10
)
325 Biogeochemical Cycling of Chemicals
Because of its position and relatively high pollution loading, the
North Sea is a focus of considerable interest. An inventory of inputs
of trace metals (e.g. Pb, Cd, Zn, Cu, etc.) accords similar importance to
riverine inputs and atmospheric deposition.
14
Controls have been ap-
plied to many source categories and total inputs of the metals indicated
have in general declined appreciably. One particular example is lead, for
which most European countries introduced severe controls on use in
gasoline (petrol) during the 1980s and a total ban in 2000; atmospheric
concentrations have fallen accordingly. Although the data are less clear,
it might be anticipated that concentrations in river water will also
decline as a result of reduced inputs from direct atmospheric deposition
and in runoff waters from highways and land surfaces.
As explained in Chapter 4, the sea may be both a source and a sink of
trace gases. The direction of flux is dependent upon the relative con-
centration in air and seawater.
15
If the concentration in air is C
a
, the
equilibrium concentration in seawater, C
w (equ)
is given by
C
w(equ)
¼ C
a
H
À1
(7.10)
where H is the Henry’s Law Constant. The Henry’s Law Constant can
be expressed as follows:
H ¼
p
s
S
aq
100
100
10
10
1
1
0.1
0.1
0.01
0.01
0.001
0.001
Diameter of unit density particle d
p
(µm)
D
r
y

d
e
p
o
s
i
t
i
o
n

v
e
l
o
c
i
t
y

V
d
,

(
c
m

s

1
)
Mean windspeed 10 m s
−1
Mean windspeed 5 m s
−1
Figure 4 Calculated values of deposition velocity to water surfaces as a function of
particle size and wind speed
326 Chapter 7
where p
s
¼ saturation vapour pressure and S
aq
¼ equilibrium solubility
in water.
Worked example
For benzene
p
s
¼ 12.7 kPa at 251C
S
aq
¼ 1:78 g L
À1
¼
1:78 Â 1000
78
¼ mol m
À3
Calculate H for benzene at 251C.
For benzene
H ¼
p
s
S
aq
H ¼
12:7 Â 10
3
ð1:78 Â 10
3
Þ=78
¼556 Pa m
3
mol
À1
Figure 5 Spatial distribution of zinc concentrations (in ng m
À3
) in air over the North Sea
during 1989
(From Ottley and Harrison.
13
)
327 Biogeochemical Cycling of Chemicals
If C
w
is the actual concentration of the dissolved gas in the surface
seawater and
C
w
¼ C
(equ)
the system is at equilibrium and no net transfer occurs. If, however,
there is a concentration difference, DC, where
DC ¼ C
a
H
À1
À C
w
there will be a net flux. If
C
a
H
À1
4 C
w
the water is sub-saturated with regard to the trace gas and transfer
occurs from air to water. Conversely, gas transfers from supersaturated
water to the atmosphere if
C
a
H
À1
o C
w
The rate at which gas transfers occurs is expressed by
F ¼ K
(T)w
DC
where K
(T)w
is termed the total transfer velocity. This can be broken
down into component parts as follows:
1
K
ðTÞw
¼
1
ak
w
þ
1
Hk
a
¼ r
w
þ r
a
where k
a
and k
w
are the individual transfer velocities for chemically
unreactive gases in air and water phases, respectively and a (¼k
reactive
/
k
inert
) is a factor that quantifies any enhancement of gas transfer in the
water due to chemical reaction. The terms r
w
and r
a
are the resistances to
transfer in the water and air phases, respectively, and are directly
analogous to the resistance terms in Equation (7.8). For chemically
reactive gases, usually r
a
cr
w
and atmospheric transfer limits the overall
flux. For less reactive gases the inverse is true and K
(T)w
R k
w
; the
resistance in the water is the dominant term.
Much research has gone into evaluating k
w
and K
(T)w
, both in theo-
retical models, and in wind tunnel and field studies. The results are
highly wind speed dependent due to the influence of wind upon the
surface state of the sea. The results of some theoretical predictions and
experimental studies
16
for CO
2
(a gas for which k
w
is dominant) are
shown in Figure 6.
In addition to dry deposition, trace gases and particles are also
removed from the atmosphere by rainfall and other forms of precipita-
tion (snow, hail, etc.), entering land and seas as a consequence. Wet
deposition may be simply described in two ways. First,
328 Chapter 7
1
K
ðTÞw
¼
1
ak
w
þ
1
Hk
a
¼ r
w
þ r
a
Typical values of scavenging ratio
17
lie within the range 300–2000.
Scavenging ratios are rather variable, dependent upon the chemical
nature of the trace substance (particle or gas, soluble or insoluble, etc.)
and the type of atmospheric precipitation. Incorporation of gases and
particles into rain can occur both by in-cloud scavenging (also termed
rainout) and below-cloud scavenging (termed washout).
Numerical modellers often find it convenient to describe wet deposi-
tion by a scavenging coefficient, actually a first order rate constant for
9 8 7 6 5 4 3 2
Beaufort
80
70
60
50
40
30
20
10
0
0 5 10 15 20 25
4
8
12
16
Wind speed (m s
−1
)
(
1
0

5

m

s

1
)
T
r
a
n
s
f
e
r

v
e
l
o
c
i
t
y

(
c
m

h

1
)
Figure 6 Air–sea transfer velocities for carbon dioxide at 201C as a function of wind
speed at 10 m (m s
À1
or Beaufort Scale). The graph combines experimental
data (points) and a theoretical line
(From Watson et al.
16
) (Reprinted by permission from Nature (London),
349, 145; Copyrightr 1991 Macmillan Magazines Ltd.)
329 Biogeochemical Cycling of Chemicals
removal from the atmosphere. Thus, for trace substance A,
d½AŠ
dt
¼ ÀL½AŠ
where L is the washout coefficient, with units of s
À1
. A typical value of L
for a soluble substance is 10
À4
s
À1
although actual values are difficult to
measure and are highly dependent upon factors such as rainfall inten-
sity.
7.3 TRANSFER IN AQUATIC SYSTEMS
When rain falls over land some drain off the surface directly into surface
water courses in surface runoff. A further part of the incoming rainwater
percolates into the soil and passes more slowly into either surface waters
or underground reservoirs. Water held in rock below the surface is
termed groundwater, and a rock formation that stores and transmits
water in useful quantities is termed an aquifer. Water that passes
through soil or rock on its way to a river is chemically modified during
transit, generally by addition of soluble and colloidal substances washed
out of the ground. Some substances are removed from the water; for
example, river water often contains less lead than rainwater; one mech-
anism of removal is uptake by soil.
River waters carry both dissolved and suspended substances to the
sea. The concentrations and absolute fluxes vary tremendously. The
suspended solids load is largely a function of the flow in the river, which
influences the degree of turbulence and thus the extent to which solids
are held in suspension and resuspended from the bed, once deposited.
Table 3 shows a comparison of ‘average’ riverine suspended particulate
Table 3 A comparison of the concentration of major elements in ‘average’
riverine particulate material and surficial rocks
Element
Concentrations (g kg
À1
)
Riverine particulate material Surface rocks
Al 94.0 69.3
Ca 21.5 45.0
Fe 48.0 35.9
K 20.0 24.4
Mg 11.8 16.4
Mn 1.1 0.7
Na 7.1 14.2
P 1.2 0.6
Si 285.0 275.0
Ti 5.6 3.8
330 Chapter 7
matter and surficial rock composition
18
for the major elements. Ele-
ments resistant to chemical weathering or biological activity (e.g. alu-
minium, titanium, iron, phosphorus) show some enrichment in the
riverine solids, while more soluble elements are subject to weathering
and are depleted in the solids, being transported largely in solution
(sodium, calcium). Some pollutant elements such as the metals lead,
cadmium, and zinc tend to be highly enriched in the solids relative to
surficial rocks or soils due to inputs from human activities.
The dissolved components of river water typically exhibit significantly
higher concentrations than in rainwater
19
(Table 4), due to leaching from
rocks and soils. Some insight into the processes governing river water
composition may be gained from Figure 7. Starting from the point of
lowest dissolved salts concentrations, the ratio of Na/(Na þ Ca) appro-
aches one. This is similar to rainwater, and is termed the precipitation
dominance regime. It is typified by rivers in humid tropical areas of the
world with very high rainwater inputs and little evaporation. As the
dissolved solids concentration increases the ratio Na/(Na þ Ca) declines,
indicating an increasing importance for calcium in the rock dominance
regime. Here, increased weathering of rock provides the major source of
dissolved solids. As dissolved solids increase further, the abundance of
calcium decreases relative to sodium as the water becomes saturated with
respect to CaCO
3
, and this compound precipitates. Waters in the evap-
oration/precipitation regime are typified by rivers in very arid parts of
the world (e.g. River Jordan) and the major seas and oceans of the
world.
20,21
In total, the rivers of the world carry around 4.2 Â 10
12
kg per
year of dissolved solids to the oceans and 18.3 Â 10
12
kg per year of
suspended solids.
Table 4 Average concentrations of the major constituents dissolved in rain and
river water
Constituent
Concentrations (mg L
À1
)
Rain water River water
Na
1
1.98 6.3
K
1
0.30 2.3
Mg
21
0.27 4.1
Ca
21
0.09 15
Fe 0.67
Al 0.01
Cl
À
3.79 7.8
SO
4

0.58 11.2
HCO
3
À
0.12 58.4
SiO
2
13.1
pH 5.7
331 Biogeochemical Cycling of Chemicals
In slow-moving water bodies such as lakes and ocean basins, suspended
solids falling to the bottom produce a well-stratified layer of bottom
sediment. This is stratified in terms of age with the oldest sediment at the
bottom (where when suitably pressurised in can form rock) and the
Major oceans
Black
Baltic
Caspian
Jordan
Colorado
Volga
Yukon
Mississippi
Ganges
Congo
Columbia
Orinoco
Tefé
Negro
Sea
water
Evaporation
crystallisation
Series
Rock dominance
Series
Precipitation
dominance
1.0 0.8 0.6 0.4 0.2
Weight Na
+
Weight (Na
+
+ Ca
2+
)
10
4
10
3
10
2
10
1
10
4
10
3
10
2
10
1
T
o
t
a
l

d
i
s
s
o
l
v
e
d

s
o
l
i
d
s

(
m
g

L

1
)
(a)
(b)
Figure 7 The chemistry of the Earth’s surface waters: (a) typical values of the ratio Na
1
/
(Na
1
þ Ca
21
) as a function of dissolved solids concentrations from various
major rivers and oceans and (b) the processes leading to the observed ratios
(From Gibbs
20
) copyrightr 1970, American Association for the Advance-
ment of Science
332 Chapter 7
newest at the top, in contact with the water. If burrowing organisms do
not provide too much disturbance (termed bioturbation), the sediment
can preserve a record of depositional inputs to the water body. An
example is provided by Figure 8 in which lead is analysed in sediment
core dated from its radioisotope content.
22
The concentration rises from a
background around the year 1800, corresponding to the onset of indus-
trialisation. Considerably increased deposition is seen after 1930 due
to the introduction of leaded petrol. While some of the lead input is
via surface waters, the majority probably arises from atmospheric depo-
sition.
7.4 BIOGEOCHEMICAL CYCLES
A general model of a biogeochemical cycle appears in Figure 9. Al-
though biota are not explicitly included, their role is a very important
one in mediating transfers between the idealised compartments of the
model. For example, the role of marine phytoplankton in transferring
sulfur from the ocean to the atmosphere in the form of dimethyl sulfide
has been highlighted in Chapter 4. Biota play a major role in determin-
ing atmospheric composition. Photosynthesis removes carbon dioxide
from the atmosphere and replenishes oxygen. In a world without biota,
lightning would progressively convert atmospheric oxygen into nitrogen
oxides and thence to nitrate, which would reside in oceans. Biota also
exert more subtle influences. In aquatic sediments, micro-organisms
often deplete oxygen more quickly than it can be replenished from the
overlying water, producing anoxic conditions. This leads to chemical
Figure 8 Lead profile in a lake sediment in relation to depth and the year of incorporation
(From Davies and Galloway.
22
)
333 Biogeochemical Cycling of Chemicals
reduction of elements such as iron and manganese, which has implica-
tions for their mobility and bioavailability.
Biological reduction processes in sediments may be viewed as the
oxidation of carbohydrate (in its simplest form CH
2
O) with accompa-
nying reduction of an oxygen carrier. In the first instance, dissolved
molecular oxygen is used. The reaction is thermodynamically favoured,
as reflected by the strongly negative DG.
CH
2
O þ O
2
-CO
2
þ H
2
O DG ¼ À125.5 kJ mol
À1
e
À
When all of the dissolved oxygen is consumed, anaerobic organisms take
over. Initially, nitrate-reducing bacteria are favoured
2CH
2
O þ NO
À
3
þ 2H
1
-2CO
2
þ H
2
O þ NH
þ
4
DG ¼ À82.2 kJ mol
À1
e
À
Once the nitrate is utilised, sulfate reduction takes over
SO

4
þ H
1
þ 2CH
2
O -HS
À
þ 2H
2
O þ 2CO
2
DG ¼ À25.6 kJ mol
À1
e
À
3,4
3,4
5
5
7 6
1
2
Atmosphere
Oceans
Freshwater
Land
Marine sediment/
rock
Figure 9 Schematic diagram of the major fluxes and compartments in a biogeochemical
cycle: (1) runoff; (2) streamflow; (3) degassing; (4) particle suspension; (5)
wet and dry deposition; (6) sedimentation and (7) remobilisation
334 Chapter 7
Finally, methane-producing organisms dominate in a sediment depleted
in oxygen, nitrate, and sulfate.
2CH
2
O -CH
4
þ CO
2
DG ¼ À23.5 kJ mol
À1
e
À
Thus highly anoxic waters are commonly sources of hydrogen sulfide,
H
2
S, from sulfate reduction and of methane (marsh gas). The formation
of sulfide in sediments has led to precipitation of metal sulfides over
geological time, causing accumulations of sulfide minerals of many
elements, e.g. PbS, ZnS, HgS, etc.
7.4.1 Case Study 1: The Biogeochemical Cycle Of Nitrogen
Nitrogen has many valence states available and can exist in the envi-
ronment in a number of forms, depending upon the oxidising ability of
the environment. Figure 10 indicates the most important oxidation
states and the relative stability (in terms of free energy formation).
23
The oxides of nitrogen represent the most oxidised and least thermody-
namically stable forms. These exist only in the atmosphere. Ammonia
can exist in gaseous form in the atmosphere but rather rapidly returns to
the soil and waters as ammonium, NH
4
1
. Fixation of atmosphere N
2
by
leguminous plants leads to ammonia, NH
3
. In aerobic soils and aquatic
systems, NH
3
and NH
4
1
are progressively oxidised by micro-organisms
via nitrite to nitrate. The latter is taken up by some biota and used as a
nitrogen source in synthesising amino acids and proteins; the most
thermodynamically stable form of nitrogen. After the death of the
organism, microbiological processes will convert organic nitrogen to
ammonium (ammonification), which is then available for oxidation or
use by plants. Conversion of ammonia to nitrate is termed nitrification,
while denitrification involves conversion of nitrate to N
2
.
Figure 11 shows an idealised nitrogen cycle. The numbers in boxes
represent quantities of nitrogen in the various reservoirs, while the arrows
show fluxes.
23
It is interesting to note that substances involving relatively
small fluxes and burdens can have a major impact upon people. Thus
nitrogen oxides, NO, NO
2
, and N
2
O are very minor constituents relative
to N
2
but play major roles in photochemical air pollution (NO
2
), acid rain
(HNO
3
from NO
2
), and stratospheric ozone depletion (N
2
O).
Nitrate from fertilisers represents a very small flux but has major
implications in terms of eutrophication of surface waters.
7.4.2 Case Study 2: Aspects of Biogeochemical Cycle of Lead
Lead is a simpler case to study than nitrogen due to the small number of
available valence states. The major use of lead until recently was a
335 Biogeochemical Cycling of Chemicals
tetraalkyl lead gasoline additives in which lead is present as Pb
IV
. The
predominant compounds used were tetramethyl lead, Pb(CH
3
)
4
, and
tetraethyl lead, Pb(C
2
H
5
)
4
. These are lost to the atmosphere as vapour
from fuel evaporation and exhaust emissions from cold vehicles, but
comprised only 1–4% of lead in polluted air.
2
Leaded gasoline also
contains the scavengers 1,2-dibromoethane, CH
2
BrCH
2
Br, and 1,2-di-
chloroethane, CH
2
ClCH
2
Cl, which convert lead within the engine to
lead halides, predominantly lead bromochloride, PbBrCl, in which lead
is in the Pb
II
valence state, its usual form in environmental media. About
75% of lead alkyl burned in the engine is emitted as fine particles of
inorganic lead halides. Atmospheric emissions of lead arise also from
industry; both these and vehicle-emitted lead have declined massively.
Figure 12 shows trends in United Kingdom emissions of lead to
Oxidation
state
Free energy
of formation
∆G
less stable
positive
0
negative
more stable
Oxides of nitrogen
dinitrogen oxide
nitric oxide
nitrogen dioxide
N
2
O
NO
2
NO
Reactions
1 fixation
2 nitrification
3 assimilation by piants
4 ammonification
5 denitrification
6 nitrate-containing precipitation often
as nitric acid in acid rain
micro-organisms play a part in reactions 1, 2, 4 and 5
+1
+3
+4
0
−3
−3
+3
+5
N
2
dinitrogen
NH
3
ammonia
NO

2
nitrite
NO

3
nitrate
amino acids,
proteins
3
4
3 2
2
5
5
5
6
Figure 10 Chemical forms and cycle of nitrogen
(From O’Neill.
23
)
336 Chapter 7
atmosphere from leaded petrol upto 1996, since when emissions from
leaded petrol have declined almost to zero.
24
Lead emitted to the
atmosphere has a lifetime of around 7–30 days and hence may be
subject to long-range transport. Concentrations of trace elements in
polar ice provide a historical record of atmospheric deposition. Meas-
urements (Figure 2) have shown a marked enhancement in lead accom-
panying the increase in leaded gasoline usage, and a major decline in
recent years attributable to reduced emissions to atmosphere.
Atmospheric lead is deposited in wet and dry deposition. Lead is
relatively immobile in soil, and agricultural surface soils in the UK
exhibit concentrations approximately double those of background soil,
which contain ca. 15–20 mg kg
À1
derived from soil parent materials,
other than in areas of lead mineralisation where far greater concentra-
tions can be found. Local perturbations to the cycle of lead can be
important. For instance, the lead content of garden soils correlates
strongly with the age of the house. This is probably due to the deteri-
oration of leaded paintwork on older houses and the former practices of
disposing of household refuse and fire ashes in the garden. Lead is also
of low mobility in aquatic sediments and hence the sediment may
provide a record of historical lead deposition (see Figure 8).
NH
3
/NH
4
+
N
2
N
2
O / NO / NO
2
30
80 20
1300
90
120
4.1 × 10
9
1.3 × 10
4
90
2
30
25
80
fertiliser
biomass
× 10
9
kg N
× 10
9
kg N a
−1
8 × 10
8
5 × 10
2
3 × 10
5
2 × 10
8
SEDIMENTS-
Organic
compounds
Inorganic compounds
30
30
biomass
dissolved N
compounds
SEDIMENT
reservoirs fluxes
Figure 11 Schematic representation of the biogeochemical cycle of nitrogen, indicating
the approximate magnitude of fluxes and reservoirs
(After O’Neill.
23
)
337 Biogeochemical Cycling of Chemicals
Plants can take up lead from soil, thus providing a route of human
exposure. Careful research in recent years has established transfer
factors, terms the Concentration Factor (CF), where
CF ¼
D Concentration of lead in plant ðmg kg
À1
dry wt:Þ
D Concentration of lead in soil ðmg kg
À1
dry wt:Þ
The value of CF for lead is lower than for most metals and is typically
within the range 10
À3
À 10
À2
. Much higher values had been estimated
from earlier studies, which ignored the importance of direct atmospheric
deposition as a pathway for contamination. The direct input from the
air to leaves of plants is often as great, or greater than soil uptake.
24,25
This pathway may be described by another transfer factor, termed the
Air Accumulation Factor (AAF), where
AAFðm
3
g
À1
Þ ¼
D Concentration of lead in plant ðmg g
À1
dry wt:Þ
D Concentration of lead in air ðmg m
À3
Þ
Values of AAF are plant dependent, due to differences in surface
characteristics, but values of 5–40 are typical.
25,26
Thus, a plant grown
on an agricultural soil with 50 mg kg
À1
lead will derive 0.25 mg kg
À1
dry
weight lead from the soil (CF ¼ 5 Â 10
À3
), while airborne lead of 0.1 mg
m
À3
will contribute 2.0 mg g
À1
(Rmg kg
À1
) of lead (AAF ¼ 20 m
3
g
À1
).
Thus, in this instance airborne lead deposition is dominant. The air lead
concentration of 0.1 mg m
À3
was typical of rural areas of the UK until
1985. Since that time, the drastic reduction of lead in gasoline has led to
appreciably reduced lead-in-air concentrations in both urban and rural
localities.
Human exposure to lead arises from four main sources:
2,27
(i) Inhalation of airborne particles. The adult human respires ap-
proximately 20 m
3
of air per day. Thus for an urban lead
concentration of 0.1 mg m
À3
, intake is 2 mg per day. This is rather
efficiently absorbed (ca. 70%) and therefore uptake is around 1.4
mg per day in this instance.
(ii) Indigestion of lead in foodstuffs. The concentrations of lead in
food obviously vary between different foodstuffs and even be-
tween different batches of the same food. Typical fresh weight
concentrations (much of the weight of some foods is water) are
from 10 to 50 mg Pb kg
À1
. Thus a food consumption of 1.5 kg per
day represents an intake of around 50 mg per day and an uptake
(10–15% efficient) of around 6 mg per day.
(iii) Drinking water and beverages. Concentrations of lead in drink-
ing water vary greatly, related particularly to the presence or
338 Chapter 7
absence of lead in the household plumbing system. Most house-
holds in the UK conform to the EC standard of 50 mg L
À1
and a
concentration of 4 mg L
À1
may be taken as representative. Gas-
trointestinal absorption of lead from water and other beverages is
highly dependent upon food intake. After long fasting, absorp-
tions of 60–70% have been recorded, 14–19% with a short period
of fasting before and after the meal, and only 3–6% for drinks
taken with a meal. If 15% is taken as typical, for a daily
consumption of 1.5 L, intake is 7.5 mg and uptake 1.1 mg.
(iv) Cigarette smoking exposes the individual to additional lead.
While both individual exposure to lead and the uptake efficiencies of
individuals are very variable, it is evident that exposure arises from a
number of sources and control or human lead intake, if deemed to be
desirable, requires attention to all of those sources. An additional
pathway of exposure, not easily quantified, and not included above is
ingestion of lead-rich surface dust by hand-to-mouth activity in young
children.
The above calculations estimate that for a typical adult in a developed
country, daily uptake of lead from air, diet, and drinking water is,
respectively 1.4 mg, 6 mg, and 1.1 mg. Exposure to lead from all of these
sources has fallen rapidly over the past 20–30 years. Figure 12 contrasts
the temporal trends in use of lead in petrol (gasoline) and blood leads in
the general population of the UK over the period when much of this
decline took place. It is interesting to note that from 1971 to 1985 use of
lead in petrol was relatively steady, but blood leads declined by a factor
of more than two over this period mainly as a response to reductions in
dietary exposure, particularly associated with the cessation of use of
25
20
15
10
5
0
1970 1974 1978 1982 1986 1990 1994
Year
0
2
4
6
8
10
12
G
a
s
o
l
i
n
e

L
e
a
d

(
T
h
.

T
o
n
n
e
s
)
B
l
o
o
d

L
e
a
d

(
µ
g

/

d
L
)
Blood Lead
Gasoline Lead
Figure 12 Trends in lead use in petrol (gasoline) and of lead in the blood of the general
population in the United Kingdom, 1970–1995
339 Biogeochemical Cycling of Chemicals
leaded solder to seal food cans. A dramatic reduction in gasoline lead
usage occurred at the end of 1985 when the maximum permissible lead
content of petrol was reduced from 0.4 g L
À1
to 0.15 g L
À1
, and there
has been a steady reduction in lead use since, with the increases in
market penetration of unleaded fuel, until it became mandatory in the
year 2000. Despite the ability of a vehicle emitting lead to cause direct
lead exposure through the atmosphere, as well as indirect exposure
through contamination of food and water, the lack of any obvious step
change in blood lead associated with the reduction of lead in petrol
shows clearly that at that time leaded petrol was not a major source of
direct exposure for the general population.
7.5 BEHAVIOUR OF LONG-LIVED ORGANIC CHEMICALS IN
THE ENVIRONMENT
A very large number of organic chemicals are manufactured and have a
wide variety of uses. In most cases of manufacture, distribution or use,
some of the chemical becomes released and dispersed in the environment.
In some instances, the chemical is highly reactive and degrades very
rapidly; often the main mechanism is breakdown by bacteria or other
organisms and there are standard tests to evaluate the biodegradability of
synthetic chemicals. On the other hand, many such chemicals, in order to
be useful in products, are relatively long-lived and hence may be persistent
within the environment. This raises the question of which environmental
compartment (air, water, soil, etc.) the chemical will partition into pre-
dominantly. Such knowledge is critical to predicting possible environ-
mental effects and directing monitoring programmes. Over the past few
years Mackay and colleagues
28
have developed methods for predicting the
behaviour of chemicals released into the environment and at the simplest
level, these are based solely upon an assumption of equilibrium parti-
tioning between the various environmental compartments. The basic
principles are described in Chapter 6, and this section is concerned with
how these methods are applied in a practical way.
The approach depends upon assuming a model environment consist-
ing of specified volumes of air, water, soil, and sediment (see Table 5).
Within those compartments, there are other components such as parti-
cles in water, fish, or soil solids, and some of these are assumed to
contain an organic fraction of defined abundance (see Table 5). The
presence of this organic matter is important since most organic com-
pounds will preferentially partition into an organic-rich medium.
Having defined a model environment, partitioning between the vari-
ous compartments is predicted on the basis of equilibrium relationships,
340 Chapter 7
which relate to the fundamental physico–chemical properties of the
organic chemical under consideration. Important in this context is the
Henry’s Law constant, which describes the equilibrium partitioning
between air and water that is defined as
H ¼ K
aw
¼
p
C
W
¼
p
s
S
aq
where p is the vapour pressure in air
C
W,
the concentration in water,
S
aq
, the equilibrium aqueous solubility, and
p
s
, the saturation vapour pressure for the pure substance.
Partition between compartments within the aqueous environment is
typically described through the octanol–water partition coefficient, K
ow
,
or the organic carbon–water partitioning coefficient, K
oc
(see Chapter 5).
This approach assumes that partitioning from water into fish or sus-
pended solids within the water is determined by the availability of organic
matter whose properties as a solvent can be described by a parallel with
octanol for which partitioning data are widely available
K
ow
¼
Concentration in octanol
Concentration in water at equilibrium
Table 5 Properties of a ‘‘model world’’ for modelling the behaviour of organic
chemicals
28
Area (m
2
) Depth (m) Volume (m
3
) Advective residence Time (h)
Air 10
11
1000 10
14
100
Water 10
10
20 2 Â 10
11
1000
Soil 9 Â 10
10
0.2 1.8 Â 10
10
Sediment 10
10
0.05 5 Â 10
8
50,000
Volume fractions
Organic carbon or
lipid mass fraction
Density,
kg m
À3
Aerosol 2 Â 10
À11
2000
Particles in water 5 Â 10
À6
0.2 1500
Fish 10
À6
0.5 1000
Soil pore air 0.2
Soil pore water 0.3
Soil solids 0.5 0.02 2400
Sediment pore water 0.8
Sediment solids 0.2 0.04 2400
341 Biogeochemical Cycling of Chemicals
A further partition coefficient is the octanol–air partition coefficient,
which can be used to describe the partitioning between the organic matter
in soil, for which octanol is taken as a surrogate, and the atmosphere.
Thus,
K
oa
¼
concentration in octanol
concentration in air at equilibrium
Values of these partition coefficients have been measured for a wide
variety of substances, but for those which measurements have not been
made, there are methods of calculation based upon fundamental proper-
ties of the molecule.
Frequently, the organic matter comprises only a fraction, f, of the
medium. Therefore for partition between air and soil containing 20%
organic matter content
K
oa
¼
concentration in organic matter
concentration in air
¼
C
om
p
¼
C
soil
fp
and C
soil
¼ K
oa
fp ¼ 0.2 K
oa
.p
Worked example
What concentration of naphthalene in a soil of 20% organic matter
will be in equilibrium with a concentration of 10 ppb vapour in air
(water solubility ¼ 31 g m
À3
; saturation vapour pressure ¼ 10.4 Pa
and log K
ow
¼ 3.37).
In a saturated system,
K
ow
¼ 2:35 Â 10
3
¼
C
octanol
31
and
C
octanol
¼ 7.28 Â 10
4
g m
À3
at equilibrium
Then,
K
oa
¼
7:28 Â 10
4
10:4
¼7:00 Â 10
3
g Pa
À1
m
À3
342 Chapter 7
A concentration of 10 ppb in air ¼ 1.013 Â 10
5
 10
À8
Pa ¼ 1.013 Â
10
À3
Pa
C
octanol
¼1:013 Â 10
5
 10
À8
Pa
¼1:013 Â 10
À3
Pa
¼1:013 Â 10
À3
Á K
oa
¼1:013 Â 10
À3
Á 7:00 Â 10
3
¼7:09 g m
À3
and
C
soil
¼0:2 Á C
octanol
¼0:2 Á 7:09
¼1:42 g m
À3
In order to calculate the equilibrium partitioning of a substance within
the model world, a mass balance exercise is conducted. Thus, for a
system comprising simply air, water, and soil, the mass balance equation
would be
M ¼V
1
C
1
þ V
2
C
2
þ V
3
C
3
¼V
1
C
1
þ V
2
C
1
K
21
þ V
3
C
1
K
31
¼C
1
ðV
1
þ V
2
K
21
þ V
3
K
31
Þ
where M is the total mass of substance and V
i
and C
i
represent,
respectively the volumes and concentrations of each medium, i.
It may be seen that by rearranging this equation, the concentration C
1
in one of the media can be estimated from knowledge of the total mass
of compound in the system, the volume of each of the three media and
the equilibrium partition coefficients between them.
It may also be seen that if the various partition coefficients are known,
then concentrations in all three compartments, C
1
, C
2
, and C
3
can be
calculated and therefore the overall distribution of the chemical within the
environment inferred. For partitioning, for example, into soil, it is assumed
that the substance partitions solely into the organic carbon fraction of the
soil solids, and since this is a relatively small percentage of the total soil, the
mass fraction of organic matter has to be included in the calculation.
343 Biogeochemical Cycling of Chemicals
This describes one of the most basic kinds of calculations, which
nonetheless can be quite powerful. More sophisticated methods, which
take account of transport times within the environment and breakdown
rates of chemicals are also available. Such models are widely used in
predicting the environmental fate of organic chemicals.
QUESTIONS
(i) Discuss what is meant by a biogeochemical cycle, describing the
major facets and illustrating the processes involved with examples.
(ii) Discuss the temporal trends in lead emissions and concentra-
tions in the environment and how environmental media can be
used to elucidate historical trends in environmental lead.
(iii) Explain what is meant by an environmental lifetime and derive
an expression for environmental lifetime in terms of a chemical
rate constant. Compare and contrast the typical atmospheric
lifetimes of methane, nitrogen oxide, and the CFCs and explain
how this relates to the atmospheric distribution and properties
of these compounds.
(iv) Explain the processes by which trace substances can exchange
between the atmosphere and the oceans and show how rates of
exchange can be calculated. Give examples of substances whose
exchange between these media is important.
(v) Explain why the waters in rivers in different parts of the world
have differing composition and relate this to the climatology of
the region. Explain carefully what is meant by dissolved and
suspended solids and explain how both arise.
(vi) Explain the environmental pathways followed by lead emissions
from road traffic after emission to the atmosphere and explain
how this can lead to pollution of a range of environmental
media. Indicate the quantitative ways in which such transfer can
be expressed.
(vii) Estimate atmospheric lifetimes for the following:
(i) methane, if the globally and diurnally averaged concentra-
tion of hydroxyl radical is 5 Â 10
5
cm
À3
(ii) nitrogen dioxide in the middle of a summer day when the
concentration of hydroxyl radical is 8 Â 10
6
cm
À3
(iii) nitrogen dioxide at nighttime if the sole mechanism of
removal is dry deposition with a deposition velocity of 0.1
cm s
À1
, and the mixing depth is 100 m.
344 Chapter 7
(viii) If the atmospheric concentration of sulfur dioxide is 10 ppb,
calculate the following:
(i) the atmospheric concentration expressed in mg m
À3
at one
atmospheric pressure and 251C. (Use the fact that 1 mol of
any gas (64 g in the case of sulfur dioxide) occupies 22.4 L
at STP)
(ii) the deposition flux to the surface if the deposition velocity is
1.0 cm s
À1
(iii) the atmospheric lifetime with respect to dry deposition for a
mixing depth of 800 m
(iv) the atmospheric lifetime with respect to oxidation by hy-
droxyl radical if the diurnally averaged OH radical concen-
tration is 8 Â 10
5
cm
À3
and the rate constant for the SO
2
-
OH reaction is 9 Â 10
À13
cm
3
molec
À1
s
À1
(v) the lifetime with respect to wet deposition if the washout
coefficient is 10
À4
s
À1
.
(ix) Explain the thermodynamic controls on biological reduction
processes in aquatic sediments and explain how these influence
the chemical forms of nitrogen in the environment.
(x) If any organic chemical has a log K
ow
of 4.3 and a river water
concentration of 10 mg L
À1
, what concentration is predicted
to occur in fish if assumed to have a 50% organic matter
(lipid) content (assume that the fish and the water are of equal
density).
REFERENCES
1. W.H. Schroeder and D.A. Lane, Environ. Sci. Technol., 1988, 22, 240.
2. R.M. Harrison and D.P.H. Laxen, Lead Pollution: Causes and
Control, Chapman & Hall, London, 1981.
3. P. Brimblecombe, Air Composition and Chemistry, 2nd edn, Cam-
bridge University Press, Cambridge, 1996.
4. J.-P. Candelone, S. Hong, C. Pellone and C.F. Boutron, J. Geophys.
Res., 1995, 100, 16605–16616.
5. B.J. Finlayson-Pitts and J.N. Pitts Jr., Atmospheric Chemistry,
Wiley, Chichester, 1986.
6. C.N. Hewitt and R.M. Harrison, Atmos. Environ., 1985, 19, 545.
7. J.A. Garland, Proc. R. Soc. London, Ser. A, 1977, 354, 245.
8. S. Yamulki, R.M. Harrison and K.W.T. Goulding, Atmos. Environ.,
1996, 30, 109–118.
9. R.S. Cambray and J.D. Eakins, Nature, 1982, 300, 46.
10. P.A. Cawse, UKAEA Report No. AERE-9851, 1980.
345 Biogeochemical Cycling of Chemicals
11. S.A. Slinn and W.G.N. Slinn, Atmos. Environ., 1980, 14, 1013.
12. R.M. Williams, Atmos. Environ., 1982, 16, 1933.
13. C.R. Ottley and R.M. Harrison, Eurotrac ASE Annual Report,
Garmisch-Partenkirchen, 1990.
14. R.F. Critchley, Proceedings of International Conference on Heavy
Metals in the Environment, Heidelberg, Germany; CEP Consultants,
Edinburgh, 1983, 1109.
15. P.S. Liss and L. Merlivat, The Role of Air-Sea Exchange in Geo-
chemical Cycling, P. Buat-Menard (ed), Reidel, Dordrecht, 1986, 113.
16. A.J. Watson, R.C. Upstill-Goddard and P.S. Liss, Nature, 1991,
349, 145.
17. R.M. Harrison and A.G. Allen, Atmos. Environ., 1991, 25A, 1719.
18. J.M. Martin and M. Meybeck, Mar. Chem., 1979, 7, 177–206.
19. R.M. Garrels and F.T. MacKenzie, Evolution of Sedimentary Rocks,
W.W. Norton (ed), New York, 1971.
20. R.J. Gibbs, Science, 1970, 170, 1088.
21. R.M. Harrison and S.J. de Mora, Introductory Chemistry for the
Environmental Sciences, 2nd edn, Cambridge University Press,
Cambridge, 1996.
22. A.O. Davies and J.N. Galloway, Atmospheric Pollutants in Natural
Waters, S.J. Eisenreich (ed), Ann Arbor, MI, 1981, 401.
23. P. O’Neill, Environment Chemistry, George, Allen, and Unwin,
London, 1985.
24. Department of Environment, Transport and the Regions, ‘Digest of
Environmental Statistics’, No. 19, The Stationary Office Ltd., Ed-
inburgh, 1997.
25. R.M. Harrison and M.B. Chirgawi, Sci. Total Environ., 1989, 83, 13.
26. R.M. Harrison and M.B. Chirgawi, Sci. Total Environ., 1989, 83, 47.
27. Royal Commission on Environmental Pollution, ‘Ninth Report:
Lead in the Environment’, HMSO, London, 1983.
28. D. Mackay, E. Webster and T. Gouin, Partitioning, persistence and
long-range transport of chemicals in the environment, in: Chemicals
in the Environment: Assessing and Managing Risk, R.E. Hester and
R.M. Harrison (eds), Issues in Environmental Science and Tech-
nology, No. 22, Royal Society of Chemistry, Cambridge, pp 132–
153, 2006.
346 Chapter 7
Glossary
abiotic: physical or chemical processes in the environment as opposed to
biologically driven processes (biotic).
adiabatic compression: compression of a fluid without extraction of heat
resulting in increased temperature.
advection: horizontal or vertical transfer of material, heat, etc., due to
the mass movement of water in the ocean.
aeolian transport: wind-borne transfer of material.
aggregation: process of combining particulate material into larger par-
ticles.
algae: simple unicellular or multi-cellular photosynthetic plants, which
thrive in a wet environment, e.g., lakes.
alkalinity: a measure of the proton deficit in solution, which is opera-
tionally defined by titration with a strong acid to the carbonic acid end
point.
alluvium(al): unconsolidated material, consisting of weathered or eroded
particles of minerals and rocks, i.e., transported by a flowing river and
deposited at points along the flood plain of the river.
ammonification: the bacterial transformation of dissolved organic nitro-
gen (DON) into dissolved inorganic nitrogen (DIN) with the first
product being NH
3
.
amphoteric: ability of a substance to act as an acid (proton donor) or
base (proton acceptor).
androgenic: general name for any substance with male sex hormone
activity in vertebrates.
anoxic: waters devoid of oxygen because circulation is restricted verti-
cally due to thermal or saline stratification and horizontally by topo-
graphic boundaries thereby producing stagnant conditions. Examples of
this atypical marine environment are the Black Sea and Saanich Inlet
(Canada).
347
apolar compound: a molecule that does not possess functional groups
and undergoes molecular interactions that are dominated by Van-der-
Waals interactions only (e.g., n-alkanes).
aragonite: a solid phase of CaCO
3
.
authigenic: formed, e.g., minerals, in place during or after deposition of
sediment.
authigenic precipitation: solid-phase production in seawater due to a
substance exceeding its solubility product, such as the formation of
ferromanganese nodules.
bacteria: cellular microorganisms incapable of photosynthesis.
benthic: living on the bottom of a water body, e.g., lake.
bioaccumulation: the progressive increase in concentration of a substance
in an organism because the rate of intake via the body surface (e.g., from
water) or in food is greater than the organism’s ability to remove the
substance from the body.
bioavailable: the portion of a chemical substance (nutrient, metal, toxin)
that can be absorbed, transported, and utilized physiologically.
biogenic hydrocarbon: an organic compound originating from a recent
biological source, e.g., biogenic volatile organic compounds (VOCs)
emitted from vegetation.
biogenous material: matter produced by the fixation of mineral phases by
marine organisms; notable examples being calcite and opaline silica in
the marine environment.
biomagnification: a food chain or food web phenomenon, whereby a
substance or element increases in concentration at successive trophic
levels.
biomethylation: biologically induced reactions by which methyl groups
are added to metals, metalloids, and organometallic complexes, with
consequent and varied influence on the volatility, bioavailability, and
toxicity of the element concerned.
bioremediation: the use of living organisms, generally bacteria, to clean
up oil spills or remove other pollutants from soil, water, and wastewater.
calcite: a solid phase of CaCO
3
.
carbonate compensation depth (CCD): the depth at the sediment–water
interface at which no calcareous material is preserved in the sediments.
chelate: a complex formed when a central metal atom shares more than
one electron pair with a given ligand thereby forming a ring structure,
which exhibits enhanced stability largely due to the entropy effect of
releasing large numbers of molecules from the co-ordinated water
envelopes.
chelation: the formation of a chelate.
348 Glossary
chlorinity (Cl%): the chloride concentration in seawater, expressed in
g kg
À1
, as measured by Ag
1
titration (i.e., ignoring other halide contri-
butions by assuming Cl
À
to be the only reactant).
chromophore: a chemical group or moiety within a molecule that absorbs
light.
cloud condensation nuclei (CCN): small particles in the atmosphere onto
which water can condense.
conservative behaviour: the concentration of a constituent or absolute
magnitude of a property varies only due to mixing processes.
conglomerates: a group of detrital sedimentary rocks consisting of
rounded or sub-rounded fragments.
convergence: a region in which the streamlines (i.e., currents) come
together causing water to sink.
Coriolis force: the acceleration due to the earth’s rotation deflecting
moving fluids (i.e., both air and water) to the right in the northern
hemisphere and to the left in the southern hemisphere; the magnitude of
the effect is a function of latitude, being nil at the equator and increasing
towards the poles.
cyanobacteria: commonly known as blue–green algae, which are capable
of reproducing rapidly to form algal blooms in nutrient-enriched fresh-
water and, after death, of releasing toxins.
denitrification: the reduction of nitrogen species to molecular nitrogen
(N
2
), which can occur under conditions of hypoxia or anoxia.
detritus: disintegrated material of both inorganic and biological origins.
diagenesis: the collection of processes that alter the sediments following
deposition; they may be physical (compaction), chemical (cementation,
mineral segregation, ion exchange reactions), or biological (respiration).
diatoms: a class of planktonic one-celled algae with skeletons of silica.
dielectric constant: the ratio of electric flux density to electric field, which
expresses the degree of non-conductivity of different substances.
divergence: a zone in which the flow fields (i.e., currents) separate.
endocrine disruptor: an exogenous substance or mixture that alters
function(s) of the endocrine system and subsequently causes adverse
health effects in an intact organism, or its progeny, or (sub-) popula-
tions.
enrichment factor: the ratio in a sample compared to a reference
substance (i.e., a possible source) of concentration ratios of a given
element, X, to a reference element; typically Al is used as a reference
element to denote a terrestrial source and Na for a marine source.
eutrophication: over-enrichment of a water body with nutrients, resulting
in excessive growth of organisms (i.e., algal blooms) and depletion of
349 Glossary
oxygen concentrations (hypoxia or anoxia depending upon the organic
loading) in sub-surface waters and/or sediments.
flocculation: process of combining particulate material into larger par-
ticles facilitated by particle surfaces being coated with organic material.
halmyrolysis: low-temperature reactions in seawater reactions producing
secondary material from components of continental or volcanic origin;
essentially an extension of chemical weathering of lithogenous compo-
nents.
halocline: a region in the water column that exhibits a sharp change in
salinity.
hermaphroditic: having both male and female sexual organs.
humic substances: large, refractory molecules formed as a result of
decomposition of organic matter.
hydrogenous material: matter produced abiotically within the water
column.
hydrophobic: the low affinity for water or ‘water-hating tendency’ of a
chemical as measured by its octanol/water partition coefficient.
hydrothermal waters: formed when seawater circulates into a fissured
rock matrix and, under conditions of elevated temperature and pressure,
results in compositional changes in the aqueous phase occur due to
seawater–rock interactions.
hyperkeratosis: skin lesion condition, often in the form of nodules on the
palms of the hands and soles of the feet, which can be brought about by
exposure to inorganic arsenic in drinking water.
hyperpigmentation: in the case of chronic arsenic poisoning, a finely
freckled, ‘raindrop’ pattern of pigmentation that is particularly pro-
nounced on the trunk and extremities.
hypolimnion: the stratum of water below the thermocline.
hypoxia: waters that are deficient in oxygen.
imposex: the imposition of male sex organs on female marine gastro-
pods, notably resulting from exposure to tributyltin compounds.
ion pair: the transient coupling of a cation and anion, formed by the
collision of oppositely charged ions due to electrostatic attraction,
during which each ion retains its own co-ordinated water envelope.
isopycnal: line (imaginary or on a chart) or an imaginary surface
connecting points, which have the same density.
latent heat of evaporation: the heat required (or released) to convert a
unit mass of a substance from a liquid to a gas state (or from gas to
liquid) at the same temperature and pressure.
latent heat of fusion: the heat required (or released) to convert a unit
mass of a substance from a solid to the liquid state (or from liquid to
solid) at the same temperature and pressure.
350 Glossary
ligand: a moiety acting as a Lewis base that shares a pair of electrons
with a metal atom thereby forming a complex; ligands can be neutral
(e.g., H
2
O) or anionic (e.g., Cl
À
, HCO
3
À
) species.
lithogenous material: substances coming from the continents as a result
of weathering processes; the most important components being quartz
and the clay minerals (kaolinite, illite, montmorillonite, and chlorite).
lysocline: the depth at the sediment–water interface at which appreciable
dissolution of CaCO
3(s)
starts to occur.
marine boundary layer: lowest portion of the atmosphere (from 0.25 to
3.5 km) in contact with the ocean surface.
metallothionein: A protective protein that binds heavy metals such as
cadmium and lead thereby detoxifying such contaminants.
molal concentration: the number of moles of solute per kg of solution.
molar concentration: the number of moles of solute in a litre (dm
3
) of
solution (i.e., molarity).
molecular viscosity: small-scale internal fluid friction that is due to the
random motion of the molecules within a smooth-flowing fluid.
mutagen: a chemical substance that induces a change in the of DNA of
cells.
nitrification: the stepwise oxidation of NH
4
1
to NO
2
À
and eventually to
NO
3
À
.
nitrogen fixation: the direct uptake and assimilation of molecular nitro-
gen (N
2
) by organisms.
ocean conveyor belt: see thermohaline circulation.
ochre: a natural hydrated form of ferric oxide, often precipitated from
acid mine drainage.
oestrogenic: related to, behaving like, or causing effects similar to the
natural female sex hormone in vertebrates.
oligotrophic: a term used of lakes that are poorly productive in terms of
organic matter formed because of a low nutrient supply, i.e., the
opposite of eutrophic.
osmoregulatory: a term used of an organism that actively regulates the
osmotic concentration of its internal fluids.
oxygen compensation depth: the horizon in the water column at which
the rate of O
2
production by photosynthesis equals the rate of respira-
tory O
2
oxidation.
permeability: the capacity, e.g., of a rock, to transmit water.
petrogenic hydrocarbon: an organic compound originating from unburnt
fossil fuels.
photic zone: the upper surface of the ocean in which photosynthesis can
occur, typically taken to be the depth at which sunlight radiation has
declined to 1% of the magnitude at the surface.
351 Glossary
photosensitiser: a substance that absorbs light and subsequently initiates
a photochemical reaction or photophysical alteration in the chemical of
interest.
photosynthetically active radiation (PAR): electromagnetic energy in the
400–700 nm wavelength range that can be absorbed by chlorophyll or
other light-harvesting pigments in plants and is used for photosynthesis.
physico-chemical speciation: the various physical and chemical forms in
which an element may exist in a specified system.
phytoplankton: microscopic plants living in the oceanic water column.
phytoremediation: the use of living plants to reduce the risk posed by
contaminated soil, sludges, sediments, and groundwater by removing,
degrading, immobilizing, or containing contaminants in situ.
planetary albedo: the reflectivity of the world with respect to incident
sunlight: calm seawater (B2%), vegetated regions (10–25%), deserts
(B35%), and snow covered surfaces (B90%).
podsolization: the leaching of soluble complexes of aluminum and fer-
rous iron from the A horizon and the subsequent deposition of these
metals, together with organic matter, in the B horizon.
potential density, r
h
: the density defined on the basis of potential
temperature instead of in situ temperature.
potential temperature: the temperature that a water parcel would have if
raised adiabatically to the ocean surface.
pycnocline: a region in the water column that exhibits a sharp change in
density.
pyrolytic hydrocarbon: an organic compound originating from combus-
tion sources.
quantum yield: number of molecules of reactant consumed per photon of
light absorbed.
radiolaria: single-celled planktonic organisms that build a skeleton of silica.
Redfield ratio: the constant relative amount of nutrients taken up by
phytoplankton during photosynthesis, being 106C:16N:1P.
refractometer: instrument for measuring the indices of refraction of various
substances.
remineralisation: bacterial degradation of particulate organic nitrogen
(POC) into dissolved organic nitrogen (DON).
residence time: the average lifetime of the component in a specified system,
which is, in effect, a reciprocal rate constant.
respiration: biochemical and cellular processes within an organism by which
carbon is combined with absorbed oxygen to produce carbon dioxide.
Revelle factor (R): a resistance to the dissolution of CaCO
3(s)
by carbonic
acid indicating that the ocean is relatively well buffered against changes in
SCO
2
in response to variations in atmospheric pCO
2
.
352 Glossary
salinity (S%): a measure of the salt content of seawater; a typical value for
oceanic waters being 35 g kg
À1
.
scavenge: the process by which sinking particles remove dissolved sub-
stances (metals and organic material) by surface adsorption.
siderophore: a low molecular weight substance synthesized by a variety of
micro-organisms to sequester Fe that is often in limited supply in the
environment.
sigma-tee (r
t
): the density (actually the specific gravity and hence it is a
dimensionless number) of water at atmospheric pressure based on temper-
ature and salinity in situ.
sorption: either or both adsorption or absorption of a chemical substance to
a surface.
specific heat: the amount of heat required to raise the temperature of 1 g of
a substance by 11C.
super-saturation: the unstable state of a solution or vapour that contains
more solute or gas than its solubility or vapour pressure allows.
surface tension: the work required to expand the surface of a liquid by unit
area; the cohesive force exerted at the surface of a liquid that makes it
tend to assume a spherical shape because molecules at the surface are not
surrounded by molecules on all sides and accordingly they interact more
strongly with those directly adjacent to them on and below the surface.
surfactants: surface-active or wetting agents that decrease the surface
tension of a liquid.
thermocline: that zone between the warm surface water and colder deeper
water, e.g., of a lake, in which the temperature changes most rapidly.
thermohaline circulation: the global deepwater circulation driven by den-
sity differences, which in turn are caused by variations in salinity or
temperature.
tidal prism: the difference in the volume of water in a water body between
low and high tides.
troposphere: the lowest region of the atmosphere, extending to an altitude
of 8–18 km.
T–S diagram: a plot of temperature against salinity, with applications in
defining water masses of different origin.
turbidity currents: the muddy and turbulent flow of sediment-laden waters
along the seafloor caused by sediment slumping that transport copious
amounts of material, including coarse-grained sediments, to the deep sea.
upwelling: the transport of sub-surface water to the ocean surface.
zooplankton: animal component of the planktonic community.
353 Glossary
Subject Index
A Glossary of terms can be found on pages 347–353.
acid dissociation constant (pKa) 305
acid hydrolysis 248
acid mine drainage 126–9
acid rain 255, 335
acidification 122–9
acidity constants 90, 97
activity coefficient 83, 265–6, 267
adiabatic compression 176
adsorption 214–15
advection 145, 179, 224
aeolian transport 189, 202
aerodynamic resistance 322–3
aerosol
deposition 321
formation 199, 324
organic 280
aggregation 129, 221
air accumulation factor (AAF) 338
air-land exchange 321–3
air-sea exchange 172, 184–7, 191, 324–30
air-water partition coefficient 286, 288–91,
298
airborne particles 324, 338
albedo 197, 199
algae 129, 145–50, 212, 283
blooms 145, 147–50
macroalga 53, 55
aliphatic hydrocarbons 143, 281
alkalinity 103–5, 193–5
alkanes 225, 280–1, 283
alkenes 46
alkoxy radicals 280
alkyllead additives 139, 336
alkylphenolethoxylates (APEs) 154
alkylphenols 154
alluvium 137, 236, 238
aluminium 108–10, 123–5
aluminium oxide 246
aluminosilicate clay minerals 123, 234,
241–6
ammonia 323, 335
ammonification 335
amorphous aluminosilicates 245–6
amphiboles 239–40
amphoteric behaviour 174, 214
androgenic effects 154
anion exchange 267
anoxic 115, 189, 218–19
Antarctic
bromine explosion 52–4
currents 179–81
glacier-derived material 172
ice 317
ozone hole 63–71
seabourne litter 227
vortex 66, 68–71
APEs 154
apolar compound 303
aquatic systems, modelling 121–2
aquifer 128–31, 156
aragonite 190, 212
Arctic
bromine explosion 52–4
ice 181, 317, 337
ozone hole 65, 71
water concentrations, lindane
293–5
arsenate 130, 272
arsenic 117–18, 130–1
arsenopyrite 130
354
atmosphere
chemistry 5
conductance 323
cycle 315, 320
oxidising capacity 20
trace gases 10–11, 12–14
vertical structure 8–10, 19, 316–17
atrazine 152, 153
authigenic precipitation 142–3, 146–7,
211–12
bacteria 257, 258
base saturation 270–1
bauxite 125
BCF 287–8
Beer-Lambert law 302–3
benthic 128, 145, 222
benzene 157, 327
benzophenone-3 155
bioaccumulation 138, 284, 295
bioavailability
metal complexes 82, 125
phosphorus 146
biochemical (or biological) oxygen
demand (BOD) 150–1
bioconcentration factor (BCF) 287–8
biogenic hydrocarbon sources 10, 35–6,
46, 61, 183, 197–8, 283
biogenous 212, 213
biogeochemical cycles 170–3, 197–8, 200,
209, 216, 314–16, 333–40
biological reduction processes, sediments
334
biomagnification 138, 153
biomethylation 131, 172
bioremediation 224–5
bisphenol-A 154
blood
lead levels 132
PBDEs 307
BOD 150–1
borate 272
boundary layer resistance 323
breast milk, PDBE levels 307
brominated flame retardants (BFRs)
305–9
bromine explosion 52–4
Brønsted–Guggenheim equation 87
buffer capacity, soil 255
buffer strips, water systems 145, 148
bulk density, soil 237
c spacing 243
cadmium 132–3, 202
caesium 202, 324
calcite 190, 212
calcium 143–4, 148, 206
calcium carbonate deposition 173, 190–1,
196–7
carbamazepine 155
carbon dioxide 100–3, 189–97
Carbon Preference Index (CPI) 283
carbonate alkalinity (CA) 104–5
carbonate compensation depth (CCD)
196, 201
carbonate equilibria 100–3, 192
care products 151, 155–6, 305
catalytic cycles 53, 56–63, 69
cation exchange capacity (CEC) 216,
242–3, 250, 269–71
CCD 196, 201
CCN 197, 199
CD-MUSIC 122
CFCs 184, 317
Chapman cycle 58–9
charge balance 98–100, 103–5, 248
chelate 206
chelation 205, 208, 248, 273
chemical oxygen demand (COD) 150–1
chemical processes 1–2, 3
chemical speciation, ocean 204–10
chemical weathering 91–3
chemisorption 215, 271–3
chlor-alkali plant 144
chloramines 132
chlorinated solvents 82, 300
chlorine 59–61, 64, 67–71
chlorinity (Cl%) 178
chlorite 211, 244
chlorpyrifos 303–4
chlortoluon 152
cholesterol 151
chromate 272
chromite ore processing residue (COPR)
135
chromium 106–7, 116–17, 135–7
chromophore 302
Cl% 178
355 Subject Index
Clark Fork river basin 127–8
clay 128, 133
minerals 238–45, 259, 269
climate 8, 72, 181, 185, 197, 199, 231, 235,
314
closed aqueous system 101–3
cloud condensation nuclei (CCN) 197, 199
COD 150–1
colloids 204, 208–9
complexation 273
complexes
inorganic 96
organic 97
organometallic 273
outer and inner sphere 94–7
pH-dependent formation 105–10
soil solution 266
surface 96–7
concentration, units of 5–6
concentration factor (CF) 338
conglomerates 134
congruent dissolution 92
conservative behaviour 220
consolidated rock 238
constant ionic strength equilibrium
constant (
c
K) 89
convergence 181
copper 127, 202
coprostanol 151
Coriolis force 179
cosmogenous 212–13
Coulomb’s law 268
Criegee intermediates 46, 49
cumulative stability constants (b
n
) 95
cyanide 138–9
cyanobacteria 145, 148
2,4-D 152
Davies equation 87–9, 265
DDT 289, 295
Debye-Hu¨ ckel (limiting law) equation
85–7, 265
degradation 299–301, 315
denitrification 335
density 176–7
deposition
process 34–5, 210, 314–15, 321–3
velocity 34, 321–2, 324
DET 142
detergent metabolites 151
detritus 139, 200
DGT 142–3
diagenesis 210, 218–19
dialysis 125
diatoms 122, 199, 212
dibromoethane 336
dicamba 152
dichloroethane 336
dichloromethane (DCM) 156
dichlorprop 152
dichromate 150–1
dielectric constant 268
N,N-diethyltoluamide 151
diffuse double layer 268
dimethoate 152
dimethylarsinic acid 131
dimethylsulfide (DMS) 41–2, 44–5, 183
climatic implications 197–9
dinitrogen pentoxide 40
disinfection, water 132
dissolution 91–4, 196, 247–8
dissolved
inorganic nitrogen (DIN) 200
organic carbon (DOC) 305
organic nitrogen (DON) 200
divergence 180
DMS 41–2, 44–5, 183, 197–9
drinking water 80–1, 125, 128, 131–2
lead 338–9
nitrate 149
pesticides 151–2
dry deposition 26, 34, 50, 314–15, 322, 326
earth’s crust 234–75
eddy diffusivity, K
z
323
EF 182–3, 234, 324
electrode potential (E
H
) 111, 188, 260–1
electron activity 302
electron activity, hypothetical 110, 112,
188, 261
emission inventories 13
emulsions 224
endocrine disruptor 154–5
enrichment factor (EF)
seawater 182–3, 324
soil 234
environmental
behaviour 320
356 Subject Index
chemicals 143–5, 225, 279–310
compartments 314, 316–17, 321, 340
environmental organic chemistry (EOC) 5,
279–310
Environmental Quality Standards (EQSs)
136, 153
environmental reservoirs 170–3
equilibrium constant 89–91, 192
equilibrium criteria model (EQM) 296
estuaries 212, 216, 219–22
ethinylestradiol 154
ethylbenzene 157
ethylhexyl methoxy cinnamate 155
eutrophication 145–9
exchangeable acidity 254
exchangeable cations 240, 257, 270–1
extended DH equations 85–8
feldspars 91, 239–40
ferric sulfate 148
ferrihydrite 246
‘ferromagnesian’ minerals 240
ferromanganese nodules 211, 217–18
ferrous sulfate 136, 253
flocculation 127
fluoride 272
flux 321–4
foodstuffs, lead 338
formaldehyde 11, 24, 39
freshwater 3–4, 80–157
species distribution 97–121
frog development 153
fulvic acid 252, 282
Gapon equation 269
gastropods, marine 228–9
geochemical computer models 87, 121–2
geogenic sources 11
geothite 246
Gibbs free energy of transfer, DG 111,
292–3
Gibbs-Helmholz equation 292–3
gleys 263
global pollution problems 230,
317
gold 137–9
groundwater 80–2, 330
arsenic 130–1
chromium 135–7
nitrate 149–50
selenium 133–5
Gu¨ ntelberg approximation 86–7
Guoy-Chapman model 268
haematite 246
halmyrolysis 212, 216
halocarbons 2, 18, 36
halocline 176
halogen
chemistry 51–8
oxidation 52–3
heavy metals 127–9, 142
Henry’s Law 186, 341
constant (H) 186, 285, 288–91, 326–9,
341
hermaphroditic fish 154
hexavalent chromium 136
human lead exposure 338–9
humic acid 252, 282
humic substances 252–3, 267, 282
humin 252
humus 249
formation 249–51
fractionation 252
hydrocalumite 136
hydrocarbons 35–7
oxidation 35–7
sources 282–4
total petroleum 225
volatile (oil) 225
hydrogen bonding 174, 215,
244
hydrogenolysis 300
hydrogenous material 211–12,
216
hydrophobic 154
hydrophobic organic chemicals (HOCs)
290
hydrothermal vents 171, 204, 217
hydrous iron oxides 130
hydrous metal oxides 135
hydrous oxides 20–4, 246, 267
hydroxyapatite 148
hydroxyl radical 20–4, 297, 318–19
hyperkeratosis 130
hyperpigmentation 130
hypolimnion 146
hypoxia 189
357 Subject Index
ibuprofen 155
ice
Antarctic 317
Arctic 181, 317, 337
rafting 213
illite 211, 243
imposex 228–9
incongruent dissolution 92
inherited minerals 238
inner sphere complexation 95–6
internal loading, phosphorus 147
iodine monoxide 54–5
ion(s)
activity 83–8, 265–6
exchange 215–16, 267–71
ionic potential 183–4, 263
ionic strength 84–9, 110–21, 265–6
pair formation 266–7
Irish Sea 324, 325
iron 112–13, 119–21
biological productivity limiting 200
estuarine 221–2
iron oxides 115, 126–7, 272
hydrous oxides 130
irrigation 132–5, 150
isomorphous substitution 242
isopleth 32
isoproturon 152
isopycnals 177
Itai-Itai 133
kaolinite 211, 243
K
aw
286, 288–91, 298
K
d
286, 288
Kesterson Reservoir 135
K
oa
286, 291–2, 298, 342–3
K
ow
286, 287–8, 298, 342
lake 82, 123–5
sediment 139–49
Langmuir equation 272–3
latent heat 174, 323
leaching 257
lead 131–2, 139, 202, 317, 333
biogeochemical cycle 335–40
human exposure 338–9
lead-210 139
leaded petrol 317, 336, 339–40
lead halides 336
Leblanc process 143
lifetime(s) 25, 317–21
behavioural influence 319–21
calculation 317–19
ligand 206–7
ligand exchange 271–3
liming 132, 149, 255
lindane 152, 293–5
linuron 152
lithogenous material 210–11
long range transport 295
lysocline 196
MacInnes convention 87
magnesium 206
manganese 112, 204
manganese oxides 246
marine boundary layer 21, 34, 171–2, 179,
197
marine sediment 210–13
MCPA 152
mecoprop 152
mercury 137–8, 144–5, 207–8
mesopause 9–10
mesosphere 9–10
metallothionein 205, 208
methaemoglobinaemia 149–50
methane 315–16, 317, 318–19
methyl chloroform 319
methyl mercury 138
methyl tert-butyl ether (MTBE)
156–7
methylation 209
4-methylbenzylidene camphor 155
micas 239–40
mineral components, soil 238–46
Minimata, Japan 138
MINTEQA2 87, 121
mixed equilibrium constant
89–91
mixing times 316
MODEL V 122
‘model world’ environment 340–1
molal concentration 285
molecular viscosity 174
molybdenum 142, 145
monomethylarsonic acid 131
montmorillonite 211, 216
Montreal protocol 2, 63–4
358 Subject Index
MTBE 156–7
mutagen 300
natural organic matter 94, 97
Nernst Equation 111
NICA 122
nickel 202
nitrate 40–3, 149–50, 199, 272
nitrate radical 40–5
nitric acid 27–30, 40–4, 67–9, 322
nitrification 257, 335
nitrite 150
nitroarenes 299–300
nitrogen
biogeochemical cycling 200–1, 335, 337
eutrophication 81, 149
fixation 200
oxidation, atmospheric 26–8
in seawater 185–6, 200
nitrogen dioxide 6, 23, 318–19, 320
nitrogen oxides 11, 15–16, 26–8, 28–33,
335, 336
N-nitroso compounds 150
nitrous oxide 315
non-conservative behaviour 220
non-exchangeable acidity 254
non-methane hydrocarbons (NMHC)
30–1, 35–9
non-sea salt sulfate (NSSS) 183
4-nonylphenol 151
nonylphenol (NP) 154
North Sea 324–6
NO
x
see nitrogen oxides
NO
y
28
O
2
minimum 188–9, 196, 200
ocean(s) 170–230
circulation 179–82, 213
conveyor belt 179
see also seawater
ochre 148
octanol-air partition coefficient 286,
291–2, 298, 342–3
octanol-water partition coefficient 286,
287–8, 298, 342
oestradiol 154
17b-oestradiol 154
oestrogenic steroids 154
oestrone 154
oil slicks 223–6
oligotrophic 140, 145
olivine 239–40
ORCHESTRA 122
organic chemicals 151, 280–4, 340–4
‘model world’ environment 340–1
organic chemistry 5, 279–310
organic matter 113, 141, 150–7
natural 94, 97
soil 235, 248–53
turnover of 249–50
see also humus
organochlorine pesticides 143, 152–3,
154
organophosphorus pesticides 153, 303–4
orthophosphate 146
osmoregulation 124
outer and inner sphere complexes 94–7
outer sphere complexation 94–5
oxic-anoxic boundary 115, 189, 218–19
oxidation
atmospheric nitrogen 26–8
atmospheric sulfur 48–51
halogens 52–3
hydrocarbons 35–7
night-time 40–5
soil weathering 248
tropospheric 17, 20–5
oxidising capacity, atmosphere 20
oxygen 187–9
compensation depth 187
minimum 188–9, 196, 200
ozone
alkene interactions 46, 47
halogen interactions 52–3, 56–8
layer 14, 17–18, 58–63
production and destruction 28–40
ozone hole
Antarctic 63–71
Arctic 65, 71
PAHs 143, 225, 228, 282
PAN 28, 39–40
PAR 200
parent material, soil 235–41, 246, 270, 275,
337
particles
airborne 324, 338
estuarine 220–2
359 Subject Index
marine 210–13
surface chemistry 213–18
partitioning 284–6, 340–3
coefficients 285, 286–92, 293–5, 341
partition maps 295–9
temperature dependence 292–5
PCBs 143, 153–4, 295, 316, 320
PDBEs 143, 153–4
pe 110–21, 171, 188–9, 261
pe-pH diagrams 114–21, 209
perchloroethylene (PCE) 156
perfluorooctane sulfonates (PFOSs) 154
permanent negative charge, clay 242
permeability layers 82
permeable reactive barrier 136–8
peroxides 23, 34–5, 46
peroxy radicals 15–16, 19–23, 30, 280
peroxyacetlynitrate (PAN) 28, 39–40
persistence 295–6
persistent bioaccumlative toxins (PBTs)
284
persistent organic pollutant (POP) 295,
320
personal care products 151, 155–6, 305
pesticides 151–3
petrogenic hydrocarbon 283–4
PFOSs 154
pH 97–110, 171, 190, 194
minimum, estuary 220
pe-pH diagrams 114–21
scales 190
soil 254–9
pH-dependent
charge 246, 247, 258, 267, 269
complex formation 105–10
dissolution 142
pharmaceuticals 151, 155–6
phosphate 199, 201, 203, 264, 272
phosphorus 145–9
internal loading 147
photic zone 173, 187
photochemical transformation 209,
299–301, 302–3, 335
photodissociation 11–17
photolysis 303–5
photosensitiser 305
photostationary state (PSS) 26–8
photosynthesis 113, 147, 173, 187, 195,
303, 333
photosynthetically active radiation (PAR)
200
PHREEQC 121
PHREEQE 87
phthalates 154
physical weathering 91
physico-chemical speciation
estuary 221
sea 204–10
physisorption 267–71
phytoplankton 221
phytoremediation 135
pit lakes 129
Pitzer model 88–9
planetary albedo 197, 199
plastic debris 226–8
plasticizers 151
plutonium 324–5
podsolization 123
point of zero charge (PZC) 214
pollution 222, 223–30
cycling 315
polybrominated diphenyl ethers (PDBEs)
143, 153–4, 306–9
polychlorinated biphenyls (PCBs) 143,
153–4, 295, 316, 320
polychlorinated dibenzo-p-dioxins 143
polychlorinated dibenzofurans 143
polychlorinated naphthalenes (PCNs) 143,
291
polycyclic aromatic hydrocarbons (PAHs)
143, 225, 228, 282
pore water 4, 130, 141–2, 146, 228,
341
potential density (s
y
) 177
potential temperature 176
PPCPs 155–6
precipitation/dissolution 91–4, 273–4
precipitation reactions 91–4
primary soil minerals 238–40
primary sources 10, 21, 61–2, 128
pycnocline 177
pyrethroids, synthetic 152–3
pyrite 126–7, 130, 219
pyrolytic hydrocarbon 283–4
pyroxenes 239–40
quantum yield 16
quartz 239–40
360 Subject Index
radioisotopes 324–5, 333
radiolaria 199, 212
rain
acidity 255, 335
dissolved constituents 331
Redfield ratio 199
redox equilibria 114, 116, 118
redox intensity 110–14
redox potential 110–21, 171, 188–9, 260–1
redox reactions 110–14
seawater 204–5, 209
soil 260–1
redox-sensitive elements 114
refractometer 177
remineralisation 200
reservoirs, environmental 170–3, 316–21
residence time 173, 184, 202
resistance
aerodynamic 322–3
boundary layer 323
surface 323
total 323
respiration 187
Revelle factor (R) 196
Richmond mine 126
riverine particulate material 283, 330–1
river(s) 332
dissolved constituents 331
water 219, 330–2
rocks 5
s
y
177, 179
s
t
176–7
S% 174–9
salinity 174–9
salinization 81, 133
salt waters 4–5
saturation vapour pressure 289, 326–9
scavenging
coefficient 329–30
ratio 329
sea borne litter 227
sea(s) see ocean(s); seawater
seawater 173–9
albedo 197
constituents 182–4
dissolved gases 184–99
dissolved solids 332
nutrients 199–201
physico-chemical speciation 204–10
Standard Seawater 178
suspended particle matter (SPM) 283
trace elements 201–4
secondary soil minerals 240–6
secondary sources 10, 21, 39
sediment
estuarine 220–2
freshwater 4, 332–3
diatom records 122
metal and metalloid contamination
128, 130, 134–5, 138–45
nutrients 94, 145–9
oxic-anoxic boundary 115
perturbatory processes 139–45
pesticides 153
marine 210–13
diagenesis 218–19
silica 201
sources 171–3, 190
trace elements 201–4
water-sediment boundary 216–17
selenate 135, 272
selenide 135
selenite 135
selenium 133–5
Sellafield 324
Setschenow equation 88–9
settling 139, 145
sewage sludge 133, 300, 307
short-range order (amorphous)
aluminosilicates 245–6
siderophores 205, 208
sigma-tee (s
t
) 176–7
silicate(s) 199, 201, 203, 272
clays 267
primary soil minerals 238–40
silicic acid 93
silver 127
simazine 152
single-ion activity coefficients 83–4, 86
sinks (biogeochemical outputs) 170–3,
317–18
SIT model 88
skin cancer 130
smectites 244
smog(s) 37, 39–40
sodium 144, 205–6
soil 234–46
361 Subject Index
acidity 255–7
alkalinity 257–8
forming factors 235
mineral components 238–46
organic carbon content 253
organic matter 235, 248–53, 282
parent material 235–41, 246, 270, 275,
337
pH 254–9
processes 5, 275, 276
redox potential 260–1
reduction processes 261–3
solution 256, 259, 263–7
water and air content 237
weathering sequence 236
see also humus
solubility 93–4, 184–7, 274, 289
equilibrium solubility 327–8
solubility product 84, 93, 108, 133, 211,
259
Solvay Process 144
solvents, industrial 156
sorption 130, 145
sources (biogeochemical inputs) 170–3,
317–18
specific gravity 176–7
specific heat 174
Specific Ion Interaction Theory (SIT)
87–9
stability constant 95, 205–8
Stern model 268–9
steroids 151, 154
stratosphere 8–10, 58–71
source gases 62
sulfate 206
reduction 218–19
sulfide 126–7, 129, 130, 218–19
oxidation 257
sulfur
chemistry 46–51, 118–19
geochemical cycle 183
oxidation, atmospheric 48–51
sulfur dioxide 10, 48–51, 317
sulfuric acid 48, 67, 126–7
‘Superfund’ sites 127
supersaturation 185
surface charge 213–14
surface resistance 323
surface tension 174–5
surfactants 175, 301
surficial rocks 330–1
suspended particle matter (SPM) 283,
330–1
synthetic pyrethroids 152
2,4,5-T 152
T-S diagram 177
TBT 228–30
TDS 83
tetrabromobisphenol A (TBBPA) 306–9
tetrachloroethene 156
tetrachloroethylene 156
tetrachloromethane 156
thermocline 82, 176
thermohaline circulation 181
tidal prism 219
toluene 157
total dissolved solids (TDS) 83
transfer
in aquatic systems 330–3
gas (water-air) 328–9
velocity 186, 328–9
transport, long range 295
tributyltin (TBT) 228–30
1,1,1-trichloroethane (TCA) 156
trichloroethene (TCE) 156
trichloroethylene 156
tri(2-chloroethyl)phosphate 151
trichloromethane 156
triclosan 305
troposphere 8–10, 51
chemistry 17–20, 21
halogens 56–8
marine 191, 198–9
oxidation chemistry 20–40
Truesdell-Jones equation 87
tube wells 130
turbidity currents 213
ultraviolet (UV) light 15, 20, 58–60, 302
unconsolidated superficial deposits 238
unit layers, clay 242, 243
upwelling 180, 200–1
urban chemistry 37–40
van’t Hoff equation 293
vermiculite 243–4
vertical mixing, atmosphere 316
362 Subject Index
vinyl chloride 156
vitellogenin 154
vivianite 146
volatile organic compounds (VOC) 31–2,
37–40, 280, 302
volcanoes 211–12
volume-mixing ratio 6
vortex 66, 68–71
waste water 151–2, 155–6, 301
WATEQ4F 121–2
water
inventory, Earth’s surface 81
properties 173–7
river 219, 330–2
water meadow 145, 148
water surfaces 326
weathering 210
physical 91
ratio, oil 225–6, 283
soil sequence 236, 246–8
wet deposition 314–15
wetlands 129–30
Wheal Jane tin mine 127, 129
xylene 157
zinc 204, 324–5, 327
zooplankton 199
363 Subject Index